In-line process for producing plasticized polymers and plasticized polymer blends

ABSTRACT

A process for fluid phase in-line blending of plasticized polymers is provided. The process includes providing two or more reactor trains configured in parallel and a separator for product blending and product-feed separation, wherein one or more of the reactor trains produces one or more polymers and one or more of the reactor trains produces one or more plasticizers; contacting in at least one of the parallel reactor trains olefin monomers, catalyst systems, optional comonomers, optional scavengers, and optional diluents or solvents, at a temperature above the solid-fluid phase transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point pressure of the polymerization system and less than 1500 MPa; forming a reactor effluent including a homogeneous fluid phase polymer-monomer mixture and plasticizer-monomer mixture in each parallel reactor train; passing the reactor effluents through the separator; maintaining the temperature and pressure within the separator above the solid-fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase system including a plasticized polymer-rich blend phase and a monomer-rich phase; and separating the monomer-rich phase from the plasticized polymer-rich blend phase. The polymer-rich blend phase is conveyed to a downstream finishing stage for further monomer stripping, drying and/or pelletizing to form a plasticized polymer product blend. Suitable plasticizers for in-line production and blending include polyalphaolefin oligomers, polybutenes, low glass transition temperature polymers and combinations thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Non-Provisional Application that claims priority to U.S.Provisional Application 60/993,647 filed Sep. 13, 2007, which is hereinincorporated by reference.

FIELD

The present disclosure relates to the field of polymer blending. It moreparticularly relates to a process for in-line blending ofpolyolefin-based polymers and plasticizers in the fluid phase. Stillmore particularly, the present disclosure relates to a process forfluid-phase in-line blending of high molecular weight olefin polymerslow molecular weight, low glass transition temperature polyolefinsacting as plasticizers in the product-feed separator section of anintegrated polymerization plant operating with two or more parallelreactor trains.

BACKGROUND

Polyolefins, such as polyethylene or polypropylene, are widely used in anumber of everyday articles, machines, consumer goods, and the like.Polyolefins are relatively inexpensive to produce and are capable ofproviding a number of useful functions. Polyolefins may be formed intovarious shapes, films, laminates, and the like. Polyolefins may becoated on, or co-extruded with various substrates. Polyolefins may alsobe combined with other materials to form a structure having a pluralityof layers, each layer having a specific purpose. Laminates, for example,may comprise a plurality of layers, such as a configurationally rigidcore layer, an outer liquid-tight layer, an oxygen gas barrier such as amid-layer of aluminum foil, and/or other layers depending on applicationneeds. However, polyolefins may be too rigid and hard for the targetapplications, or cannot be extended without tear, or difficult toprocess due to their high viscosity at the processing temperature, orbecome brittle at colder temperatures due to their relatively high glasstransition temperatures. These properties may render various polyolefinsbrittle, hard, inflexible, and thus unsuitable for particular uses,particularly uses at lower temperatures or may lead to slower processingspeeds and/or excessive rejects during processing. Many applications ofpolyolefins would benefit from a polyolefin having useful propertiesover a wide range of temperatures, and under a variety of conditions. Itwould also be beneficial if the viscosity of melts could be reducedaffording better and higher speed processability in common polymerprocessing plants, such as extruders, melt blowers, etc. Such usefulproperties may include both high- and low-temperature performance in theareas of impact strength, toughness, flexibility, and the like. Theability to adjust the stiffness-toughness balance and processability ofpolyolefins is important to meeting the needs of a broad range ofapplications at a lower cost and thus to expanding the potential ofpolyolefins in delivering desired performance at a reduced cost.

In some instances, the stiffness-toughness balance may be tailored bychanging the molecular structure of polymers or by changing theircomposition (i.e. making copolymers), stereoregularity, molecularweight, etc. The stiffness-toughness balance may also be readily shiftedby making blends of polymers with different stiffness and toughness orby blending polymers and plasticizing agents, such as polyolefin fluidsand low molecular weight polymers, particularly low glass transitiontemperature polyolefin fluids and polymers. A plasticizer added to highmolecular weight, highly crystalline stiff polyolefins softens thestructure to improve the toughness of such materials. Plasticizers withlow glass transition temperature also extend the flexibility of plasticsto lower temperatures by lowering the glass transition temperature ofthe polymer-plasticizer blend. Plasticizers are also beneficial duringpolymer processing due to improvements in a number of characteristics,such as lubricity, viscosity, ease of fusion, etc. The concept ofplasticization, the benefits of using plasticizers, and the differentmethods of using plasticizers are discussed in detail in J. K. Sears, J.R. Darby, THE TECHNOLOGY OF PLASTICIZERS, Wiley, New York, 1982.Although this monograph focuses on the plasticization of poly(vinylchloride), PVC, the concepts and benefits are analogous to thoseapplicable to plasticized polyolefins.

Since the plasticizers are often fluids at ambient temperature,plasticized polymer blends are sometimes also referred to herein asfluid-enhanced polyolefins or fluid-enhanced polymers. These plasticizedpolymers may be made by a variety of methods. Plasticized polyolefinsare traditionally made by starting with polyolefin polymers andplasticizer fluids made in separate plants. Since the polymer is in itsessentially pure, fully recovered solid state, it is difficult andexpensive to blend it with a plasticizer fluid. A flexible but expensiveprocess of making them starts with the high molecular weight polymerresin component in its solid, essentially pure, fully recovered state.In one prior art process, the one or more solid polymers are firstmelted and then blended with the plasticizing fluid or low molecularweight resin, which is commonly referred to as a melt-blending process.In another prior art process, the one or more solid polymers are putinto solution with a suitable solvent before being blended with theplasticizing fluid or low molecular weight resin, which is commonlyreferred to as an off-line solution blending process. Off-line blendingto produce plasticized polyolefins has numerous issues in that itincrease processing cost. For example, melt blending is difficultrequiring high-performance blenders or extruders due to the highviscosity of polymers and the low viscosity of the plasticizing fluid.Off-line solution blending is also an expensive process due to the needfor redissolving the polymer and possibly the plasticizer blendcomponents and also due to the cost of solvent handling. Also, asmentioned before, handling plasticizers requires additional specialequipment.

As described above, polymer blends may be made by a variety of ways. Aflexible but expensive off-line process of making polymer blends usessolid polymers as starting materials, typically outside thepolymerization process that produced the polymer blend components. Thepolymer blend components are typically first melted or dissolved in asolvent and then blended. These processes are known as melt-blending andoff-line solution blending, respectively. In melt blending, the solid,often pelletized or baled, polymer blend components are first melted andthen blended together in their molten state. One of the difficultiespresented by melt blending is the high viscosity of molten polymers,which makes blending of two or more polymers difficult and oftenimperfect on the molecular level. In solution off-line blending, thesolid, often pelletized, polymer blend components are first dissolved ina suitable solvent to form a polymer solution, and then two or morepolymer solutions are blended together. After blending, solutionblending requires the extraction of solvent from the blend and drying ofthe blended polymer. Solution blending can overcome the viscosity issueassociated with melt blending, but is expensive due to the need forredissolving the polymer blend components and due to the cost of solventhandling.

The common feature of both melt blending and off-line solution blendingis that the polymer blending components are made in separate plants andthe solid polymers then are reprocessed either in a molten or in adissolved state to prepare the final polymer blend. In fact, theseoff-line blending processes are often operated by so-called compounders,generally independent of the manufacturers of the polymer blendcomponents. These processes add considerable cost to the cost of thefinal polymer blend. The production and full polymer recovery inseparate plants and subsequent reprocessing increases the costs ofproducing such blends because of the need for duplicate polymer recoverylines and because of the need for separate blending facilities and theenergy associated with their operations. Off-line solution blending alsorequires extra solvent, and facilities for polymer dissolution andsolvent recovery-recycle. Handling plasticizers for blending them withthe base polymer represents a further challenge, since plasticizers aretypically low molecular weight, low melting point fluids or softmaterials. Compounding plants are typically equipped for handlingfree-flowing pelletized components, thus are not equipped for receiving,storing, and blending fluids and/or soft, baled substances. Thedisclosed processes blend the plasticizer fluids and/or soft polymers inthe polymerization plant producing plasticized polymers for final use,or plasticized-polymer masterbatches for further compounding in stablepelletized forms, thus afford their handling in downstream processingplants without the need for special handling and without the associatedinvestment costs. For the above-outlined reasons, substantialreprocessing costs could be saved if the polymer blends could be made inone integrated polymerization plant in-line, i.e. before the recoveryand pelletizing of the solid polymer blend components. In someinstances, especially when the plasticizer is liquid at ambienttemperature, significant cost savings can also be achieved even if theplasticizer was produced in a separate plant by blending the liquidplasticizer with the polymer in its diluted state, i.e., before theviscosity-reducing components of the polymerization system, such asmonomer and the optional inert solvent/diluent, are removed from theproduct polymer or polymer blend.

The disadvantages of a separate polyolefin blending plant associatedwith the melt blending and off-line solution blending processes isalleviated with the prior art method of in-line solution blending ofpolymers using a series reactor configuration. Utilizing the seriesreactor configuration, product blending may be accomplished in thesolution polymerization reactor itself when the effluent of the firstsolution polymerization reactor is fed into the second reactor operatingat different conditions with optionally different catalyst and monomerfeed composition. Referring to the two-stage series reactorconfiguration of FIG. 1, the two different polymers made in the firstand second reactor stages are blended in the second stage yielding ablended polymer product leaving the second reactor. Such reactor seriesconfiguration may be further expanded into more than a two-stage seriesconfiguration (three or more reactors in series). Generally, a series ofn reactors may produce a blend with as many as n components or even morepresent in the effluent of the last reactor. Note that in principle,more than n components may be produced and blended in n reactors by, forexample, using more than one catalyst or by utilizing multiple zonesoperating at different conditions in one or more reactors of the seriesreactor cascade. While mixing in the downstream reactor(s) provides goodproduct mixing, particularly when the reactors are equipped with mixingdevices, e.g., mechanical stirrers, such series reactor configurationand operation presents a number of practical process and product qualitycontrol problems due to the close coupling of the reactors in thecascade. One of the most important difficulties in commercial practiceis ensuring proper blend and monomer ratios to deliver consistent blendquality. Additional complications arise when the blend components havedifferent monomer compositions, particularly when they have differentmonomer pools, such as in the case of blending different copolymers orin the case of blending homo- and copolymers. As will be shown later inthe detailed description of the disclosed processes, this is often thecase in the production of plasticized polyolefins. In such instances,either some monomers need to be converted completely before passing theeffluent to the downstream stages or need to be removed between thereactor stages. In many cases, such solutions are not practical. Also,since the monomer streams are blended, there is no option for theirseparate recovery and recycle mandating costly monomer separations inthe monomer recycle lines.

The above-outlined issues with series reactor operations are apparent tothose skilled in the art of polymer reactor engineering. Thesedifficulties are particularly significant in polymerization becauseunlike in small-molecule synthesis, reactor conditions determine notonly reactor productivities related to blend ratio, but also productproperties related to controlling the quality of the polymer blendcomponents. For example, FIGS. 2 and 3 show how reactor temperature andpressure affect polymer properties of fundamental importance, such asmolecular weight (MW) and melting behavior. Surprisingly, we found thatmonomer conversion in the reactor also influences these criticalproduct; attributes (see FIG. 4). Since in a series reactor cascade, theeffluent of an upstream reactor flows into the next downstream member ofthe reactor cascade, the residence time, catalyst concentration, andmonomer composition and thus monomer conversion in the downstreamreactor cannot be adjusted independently of the operating conditions(particularly of the flow rate) of the upstream reactor. Because of thisclose and inherent coupling of operating regimes in the reactors of theseries cascade, the correlations depicted in FIGS. 2, 3, and 4 furtherreduce the controllability, flexibility, and thus the usefulness of thein-line blending method in a series reactor configuration. Ultimately,this greatly reduces the number of blend products that can be made insuch a series reactor cascade and makes the blend quality difficult tocontrol.

Applying parallel reactors can overcome the disadvantages related to thedirect coupling of the polymerization reactors in an in-line polymerblending applying series reactors. While production flexibility isincreased, a parallel reactor arrangement necessitates the installationof blending vessels increasing the cost of the process. A need thusexists for an improved and cost-effective method of in-line blending ofpolymers and plasticizers to avoid the issues associated with theprior-art methods, such as melt blending and off-line solution blending.More particularly, a need exists for an improved in-line method ofblending polymers and plasticizers, especially for an improved in-linemethod of blending polyolefins and plasticizers, where the residencetime, monomer composition, catalyst choice, and catalyst concentrationcan be independently controlled in the polymer reactor(s) and theoptional plasticizer reactor(s) prior to the blending step. There isalso a need for a simplified and cost-effective polymer-plasticizerblending process to reduce the number of process steps and theassociated investment and operating costs in an integrated polymer andplasticizer production and blending process employing parallel reactortrains for producing the polymer-plasticizer blend components in-line,i.e. without recovering the polymer component(s) in its/(their) solidstate. Embodiments of the present invention, which follow, meet theseneeds.

SUMMARY

Provided is a process for fluid phase in-line blending of polymers andplasticizers.

According to the present disclosure, an advantageous process for in-lineblending of plasticized polymers includes: (a) providing two or morereactor trains configured in parallel and a high-pressure separatordownstream fluidly connected to the two or more reactor trainsconfigured in parallel, wherein one or more of the reactor trainsproduces one or more polymers and one or more of the reactor trainsproduces one or more plasticizers; (b) contacting in the two or morereactor trains configured in parallel 1) olefin monomers having two ormore carbon atoms 2) one or more catalyst systems, 3) optional one ormore comonomers, 4) optional one or more scavengers, and 5) optional oneor more diluents or solvents, wherein at least one of the reactor trainsconfigured in parallel is at a temperature above the solid-fluid phasetransition temperature of the polymerization system and a pressure nolower than 10 MPa below the cloud point pressure of the polymerizationsystem and less than 1500 MPa, wherein the polymerization system foreach reactor train is in its dense fluid state and comprises the olefinmonomers, any comonomer present, any diluent or solvent present, anyscavenger present, and the polymer product, wherein the catalyst systemfor each reactor train comprises one or more catalyst precursors, one ormore activators, and optionally, one or more catalyst supports, whereinthe one or more catalyst systems are chosen from Ziegler-Nattacatalysts, metallocene catalysts, nonmetallocene metal-centered,heteroaryl ligand catalysts, late transition metal catalysts, andcombinations thereof; (c) forming an unreduced polymer or unreducedplasticizer reactor effluent including a homogeneous fluid phasepolymer-monomer mixture in one or more parallel reactor trains and ahomogeneous fluid phase plasticizer-monomer mixture in one or moreparallel reactor trains; (d) passing the reactor effluents comprisingthe homogeneous fluid phase polymer-monomer mixture andplasticizer-monomer mixture from each parallel reactor train through thehigh-pressure separator for product blending and product-feedseparation; (e) maintaining the temperature and pressure within thehigh-pressure separator above the solid-fluid phase transition point butbelow the cloud point pressure and temperature to form a fluid-fluidtwo-phase system comprising a plasticized polymer-rich blend phase and amonomer-rich phase; and (f) separating the monomer-rich phase from theplasticized polymer-rich blend phase in the high pressure separator toform a plasticized polymer blend and a separated monomer-rich phase.

A further aspect of the present disclosure relates to an advantageousprocess for in-line blending of plasticized polymers including: (a)providing two more reactor trains configured in parallel and two or morehigh-pressure separators fluidly connected to the two or more reactortrains configured in parallel, wherein one or more of the reactor trainsproduces one or more polymers and one or more of the reactor trainsproduces one or more plasticizers; (b) contacting in the two or morereactor trains configured in parallel 1) olefin monomers having two ormore carbon atoms 2) one or more catalyst systems, 3) optional one ormore comonomers, 4) optional one or more scavengers, and 5) optional oneor more diluents or solvents, wherein at least one of the reactor trainsconfigured in parallel is at a temperature above the solid-fluidphase-transition temperature of the polymerization system and a pressureno lower than 10 MPa below the cloud point pressure of thepolymerization system and less than 1500 MPa, wherein the polymerizationsystem for each reactor train is in its dense fluid state and comprisesthe olefin monomers, any comonomer present, any diluent or solventpresent, any scavenger present, and the polymer product, wherein thecatalyst system for each reactor train comprises one or more catalystprecursors, one or more activators, and optionally, one or more catalystsupports, wherein the one or more catalyst systems are chosen fromZiegler-Natta catalysts, metallocene catalysts, nonmetallocenemetal-centered, heteroaryl ligand catalysts, late transition metalcatalysts, and combinations thereof; (c) forming an unreduced polymer orunreduced plasticizer reactor effluent including a homogenous fluidphase polymer-monomer mixture or plasticizer-monomer mixture in eachparallel reactor train; (d) passing the reactor effluents from one ormore of the parallel reactor trains through one or more high-pressureseparators, maintaining the temperature and pressure within the one ormore high-pressure separators above the solid-fluid phase transitionpoint but below the cloud point pressure and temperature to form one ormore fluid-fluid two-phase systems with each two-phase system comprisinga polymer-enriched phase or plasticizer-enriched phase and amonomer-rich phase, and separating the monomer-rich phase from thepolymer-enriched phase or plasticizer-enriched phase in each of the oneor more high-pressure separators to form one or more separatedmonomer-rich phases, one or more polymer-enriched phases and one or moreplasticizer-enriched phases; (e) passing the one or morepolymer-enriched phases and one or more plasticizer-enriched phases fromthe one or more high-pressure separators of (d), any unreduced polymerreactor effluents from one or more parallel reactor trains throughanother high-pressure separator for product blending and product-feedseparation; (f) maintaining the temperature and pressure within theanother high pressure separator of (e) above the solid-fluid phasetransition point but below the cloud point pressure and temperature toform a fluid-fluid two-phase system comprising a plasticizedpolymer-rich blend phase and a monomer-rich phase; and (g) separatingthe monomer-rich phase from the plasticized polymer-rich blend phase inthe high pressure separator to form a plasticized polymer blend and aseparated monomer-rich phase.

Another aspect of the present disclosure relates to an advantageousprocess for in-line blending of plasticized polymers including: (a)providing two or more reactor trains configured in parallel, ahigh-pressure separator downstream fluidly connected to the two or morereactor trains configured in parallel, and one or more storage tanks,wherein the two or more reactor trains produce one or more polymers andthe one or more storage tanks store one or more off-line producedplasticizers; (b) contacting in the two or more reactor trainsconfigured in parallel 1) olefin monomers having two or more carbonatoms 2) one or more catalyst systems, 3) optional one or morecomonomers, 4) optional one or more scavengers, and 5) optional one ormore diluents or solvents, wherein at least one of the reactor trainsconfigured in parallel is at a temperature above the solid-fluid phasetransition temperature of the polymerization system and a pressure nolower than 10 MPa below the cloud point pressure of the polymerizationsystem and less than 1500 MPa, wherein the polymerization system foreach reactor train is in its dense fluid state and comprises the olefinmonomers, any comonomer present, any diluent or solvent present, anyscavenger present, and the polymer product, wherein the catalyst systemfor each reactor train comprises one or more catalyst precursors, one ormore activators, and optionally, one or more catalyst supports, whereinthe one or more catalyst systems are chosen from Ziegler-Nattacatalysts, metallocene catalysts, nonmetallocene metal-centered,heteroaryl ligand catalysts, late transition metal catalysts, andcombinations thereof; (c) forming an unreduced polymer reactor effluentincluding a homogeneous fluid phase polymer-monomer mixture in eachparallel reactor train; (d) passing the polymer reactor effluentcomprising the homogeneous fluid phase polymer-monomer mixture from eachparallel reactor train through the high-pressure separator for productblending and product-feed separation; (e) maintaining the temperatureand pressure within the high-pressure separator above the solid-fluidphase transition point but below the cloud point pressure andtemperature to form a fluid-fluid two-phase system comprising apolymer-rich blend phase and a monomer-rich phase; (f) separating themonomer-rich phase from the polymer-rich blend phase in the highpressure separator to form a polymer blend and a separated monomer-richphase; and (g) feeding the one or more off-line produced plasticizersfrom the one or more storage tanks to the process after (c) to form aplasticized polymer blend.

A still further aspect of the present disclosure relates to anadvantageous process for in-line blending of plasticized polymersincluding: (a) providing two or more reactor trains configured inparallel and two or more high-pressure separators fluidly connected tothe two or more reactor trains configured in parallel, and one or morestorage tanks, wherein two or more of the reactor trains produce one ormore polymers and the one or more storage tanks store one or moreoff-line-produced plasticizers; (b) contacting in the two more reactortrains configured in parallel 1) olefin monomers having two or morecarbon atoms 2) one or more catalyst systems, 3) optional one or morecomonomers, 4) optional one or more scavengers, and 5) optional one ormore diluents or solvents, wherein at least one of the reactor trainsconfigured in parallel is at a temperature above the solid-fluidphase-transition temperature of the polymerization system and a pressureno lower than 10 MPa below the cloud point pressure of thepolymerization system and less than 1500 MPa, wherein the polymerizationsystem for each reactor train is in its dense fluid state and comprisesthe olefin monomers, any comonomer present, any diluent or solventpresent, any scavenger present, and the polymer product, wherein thecatalyst system for each reactor train comprises one or more catalystprecursors, one or more activators, and optionally, one or more catalystsupports, wherein the one or more catalyst systems are chosen fromZiegler-Natta catalysts, metallocene catalysts, nonmetallocenemetal-centered, heteroaryl ligand catalysts, late transition metalcatalysts, and combinations thereof; (c) forming an unreduced polymerreactor effluent including a homogenous fluid phase polymer-monomermixture in each parallel reactor train; (d) passing the reactoreffluents from one or more of the parallel reactor trains through one ormore high-pressure separators, maintaining the temperature and pressurewithin the one or more high-pressure separators above the solid-fluidphase transition point but below the cloud point pressure andtemperature to form one or more fluid-fluid two-phase systems with eachtwo-phase system comprising a polymer-enriched phase and a monomer-richphase, and separating the monomer-rich phase from the polymer-enrichedphase in each of the one or more high-pressure separators to form one ormore separated monomer-rich phases and one or more polymer-enrichedphases; (e) passing the one or more polymer-enriched phases from the oneor more high-pressure separators of (d), any unreduced polymer reactoreffluents from one or more parallel reactor trains through anotherhigh-pressure separator for product blending and product-feedseparation; (f) maintaining the temperature and pressure within theanother high pressure separator of (e) above the solid-fluid phasetransition point but below the cloud point pressure and temperature toform a fluid-fluid two-phase system comprising a polymer-rich blendphase and a monomer-rich phase; (g) separating the monomer-rich phasefrom the polymer-rich blend phase in the high pressure separator to forma polymer blend and a separated monomer-rich phase; and (h) feeding theone or more off-line produced plasticizers from the one or more storagetanks to the process after (c) to form a plasticized polymer blend.

These and other features and attributes of the disclosed processes forin-line blending of plasticized polymers and their advantageousapplications and/or uses will be apparent from the detailed descriptionthat follows, particularly when read in conjunction with the figuresappended hereto.

BRIEF DESCRIPTION OF THE DRAWINGS

To assist those of ordinary skill in the relevant art in making andusing the subject matter hereof, reference is made to the appendeddrawings, wherein:

FIG. 1 presents the process for the production of polymer blends in atwo-stage series reactor configuration (prior art);

FIG. 2 presents the effect of polymerization temperature on themolecular weight and melting point of polypropylene made insupercritical polypropylene using MAO-activated(μ-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dichloride(Q-Zr-MAO) catalyst at 207 MPa (30 kpsi);

FIG. 3 presents the effect of polymerization pressure on the molecularweight and melting point of polypropylene made in supercriticalpropylene using MAO-activated(μ-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dichloride(Q-Zr-MAO) catalyst at 120 and 130° C.;

FIG. 4 presents the effect of propylene conversion in the polymerizationof supercritical propylene using MAO-activated(μ-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dichloride(Q-Zr-MAO) at 130° C. and 69 and 138 MPa (10 or 20 kpsi, respectively);

FIG. 5 presents the effect of temperature on the activity ofMAO-activated (μ-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconiumdichloride (Q-Zr-MAO) catalyst in the polymerization of supercriticalpropylene;

FIG. 6 presents an exemplary in-line plasticized polymer blendingprocess schematic with a single separation vessel;

FIG. 7 presents an exemplary in-line plasticized polymer blendingprocess schematic with multiple separation vessels;

FIG. 8 presents an exemplary in-line plasticized polymer blendingprocess schematic with product effluent buffer tanks for improved blendratio control;

FIG. 9 presents an exemplary in-line plasticized polymer blendingprocess schematic with product effluent buffer tanks that also serve asmonomer/product separators for improved blend ratio control;

FIG. 10 presents an exemplary in-line plasticized polymer blendingprocess schematic with one slurry reactor train.

FIG. 11 presents an exemplary in-line plasticized polymer blendingprocess schematic with buffer tanks for improved blend ratio control andwith the option for additive/polymer blending component;

FIG. 13 presents cloud point isotherms for Polymer Achieve™ 1635;

FIG. 14 presents cloud point isotherms for Polymer PP 45379 dissolved inbulk propylene;

FIG. 15 presents cloud point isotherms for Polymer PP 4062 dissolved inbulk propylene;

FIG. 16 presents cloud point isotherms for Polymer Achieve™ 1635dissolved in bulk propylene;

FIG. 17 presents cloud point isotherms for Polymer PP 45379 dissolved inbulk propylene;

FIG. 18 presents cloud point isotherms for Polymer PP 4062 dissolved inbulk propylene;

FIG. 19 presents a comparison of isopleths for PP 45379, Achieve™ 1635,and PP 4062 dissolved in bulk propylene;

FIG. 20 presents a comparison of isopleths for Achieve™ 1635 andliterature data as described in J. Vladimir Oliveira, C. Dariva and J.C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627;

FIG. 21 presents a comparison of isopleths for PP 45379 and literaturedata as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto,Ind. Eng, Chem. Res. 29 (2000), 4627;

FIG. 22 presents a comparison of isopleths for PP 4062 and literaturedata as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto,Ind. Eng, Chem. Res. 29, 2000, 4627;

FIG. 23 presents a basic phase diagram for mixture of propylene monomerwith selected polymers (isotactic polypropylene—iPP, syndiotacticpolypropylene—sPP, atactic polypropylene—aPP, or propylene-ethylenecopolymer);

FIG. 24 presents a comparison of the density of supercritical propyleneat 137.7° C. with liquid propylene at 54.4° C.;

FIG. 25 presents an operating regime in accordance with the processdisclosed herein for a reactor operating in a single liquid phase;

FIG. 26 presents an operating regime in accordance with the processdisclosed herein for a reactor operating in a liquid-liquid phase; and

FIG. 27 presents an operating regime in accordance with the processdisclosed herein for a gravity separator.

FIG. 28 presents a graphical depiction of the thermodynamic definitionof binodal and spinodal boundaries.

FIG. 29 presents a phase diagram for a typical polymerization medium ofthe current invention.

DEFINITIONS

For the purposes of this disclosure and the claims thereto:

A catalyst system is defined to be the combination of one or morecatalyst precursor compounds and one or more activators. Any part of thecatalyst system can be optionally supported on solid particles, in whichcase the support is also part of the catalyst system.

Critical Properties of Pure Substances and Mixtures:

Pure substances, including all types of hydrocarbons, can exist ineither a subcritical, or supercritical state, depending on theirtemperature and pressure. Substances in their supercritical statepossess interesting physical and thermodynamic properties, which areexploited in this invention. Most notably, as supercritical fluidsundergo large changes in pressure, their density and solvency forpolymers changes over a wide range. To be in the supercritical state, asubstance must have a temperature above its critical temperature (Tc)and a pressure above its critical pressure (Pc). Mixtures ofhydrocarbons, including mixtures of monomers, polymers, and optionallysolvents, have pseudo-critical temperatures (Tc) and pseudo-criticalpressures (Pc), which for many systems can be approximated bymole-fraction-weighted averages of the corresponding critical properties(Tc or Pc) of the mixture's components. Mixtures with a temperatureabove their pseudo-critical temperature and a pressure above theirpseudo-critical pressure will be said to be in a supercritical state orphase, and the thermodynamic behavior of supercritical mixtures will beanalogous to supercritical pure substances.

Phase Behavior:

The phase of a hydrocarbon, or mixture of hydrocarbons, is a keythermodynamic property. A mixture's phase may be either solid, vapor,liquid, or a supercritical fluid. For purposes of this invention, thesupercritical fluid phase may at times simply be referred to as thefluid phase. A mixture is determined to be in the fluid phase when itstemperature exceeds its critical, or pseudo-critical temperature (Tc)and when its pressure exceeds its critical, or pseudo-critical pressure(Pc).

When mixtures change their phase by virtue of changes in temperature,pressure, and/or composition, they are said to cross phase boundaries,which may be represented as a locus of points (curves) ontemperature-pressure diagrams, where said curves apply to a mixtures ofa given composition. For purposes of this invention, the phaseboundaries between fluid and liquid phases will be called fluid-liquidphase boundaries, or cloud point curves, and transitions of temperaturesor pressures that cross these boundaries may be referred to asfluid-liquid transitions. A given point on the cloud point curve will bereferred to by its cloud point pressure. The cloud point pressure can beexperimentally determined as the pressure at which, and below which, ata given temperature, the polymerization system becomes turbid asdescribed in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng,Chem. Res. 29 (2000) 4627. For purposes of this invention and the claimsthereto, the cloud point is measured by shining a laser through theselected polymerization system in a cloud point cell onto a photocelland recording the pressure at the onset of rapid increase in lightscattering for a given temperature. For purposes of illustration, thefluid-liquid phase boundary (cloud point curve) of a typicalpolymerization medium is depicted in FIG. 29. The critical temperatures(Tc) and critical pressures (Pc) are those that are found in theHandbook of Chemistry and Physics, David R. Lide, Editor-in-Chief, 82ndedition 2001-2002, CRC Press, LLC. New York, 2001. In particular, the Tcand Pc of selected molecules are:

Pc Pc Name Tc (K) (MPa) Name Tc (K) (MPa) Hexane 507.6 3.025 Propane369.8 4.248 Isobutane 407.8 3.64 Toluene 591.8 4.11 Ethane 305.3 4.872Methane 190.56 4.599 Cyclobutane 460.0 4.98 Butane 425.12 3.796Cyclopentane 511.7 4.51 Ethylene 282.34 5.041 1-Butene 419.5 4.02Propylene 364.9 4.6 1-pentene 464.8 3.56 Cyclopentene 506.5 4.8 Pentane469.7 3.37 Isopentane 460.4 3.38 Benzene 562.05 4.895 Cyclohexane 553.84.08 1-hexene 504.0 3.21 Heptane 540.2 2.74 273.2 K = 0° C.

Phase boundaries between solids and liquids (or solids and fluids) willbe called solid-liquid (or solid-fluid) phase boundaries. Crossingsolid-liquid (or solid-fluid) phase boundaries will be calledsolid-liquid (or solid-fluid) transitions. A single point on asolid-liquid (or solid-fluid) phase boundary may be referred to assolid-liquid (or solid-fluid) transition temperature. However, many ofmixtures referred to in this invention exhibit two differentsolid-liquid (or solid-fluid) phase boundaries, depending on thedirection of the phase change. One is for melting, ie. when thedirection of phase change is from solid to liquid (or fluid), and theother is for crystallization, ie. when the direction of phase change isfrom liquid (or fluid) to solid. When it is necessary to differentiatebetween these two types of transitions, the terms melting andcrystallization will be used, and a single point on the phase boundarywill be referred to by its melting temperature or its crystallizationtemperature. For purposes of this invention and the claims thereto,solid-liquid (or solid-fluid) phase transitions of either type aredetermined by shining a laser through the selected polymerization mediumin a cell onto a photocell and recording the temperature at the onset ofrapid increase in light scattering indicating the formation of a solidphase (crystallization), or at the onset of a rapid decrease in lightscattering indicating the disappearance of a solid phase (melting). Forpurposes of illustration, solid-liquid (or solid-fluid) phase boundariesof both the crystallization and melting types for a typicalpolymerization medium are depicted in FIG. 29.

Phase Densities:

As described above, the measurement of phase boundaries is determined bymaking cloud point pressure measurements at a variety of temperaturesfor a given composition mixture, using the experimental methodsdescribed in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng,Chem. Res. 29 (2000) 4627. These phase boundary data are all that isneeded to fit Equation of State (EOS) models to predict thethermodynamic and physical properties of the individual phases, ie.fluid, liquid, solid, and/or vapor over a range of temperature andpressure. For the experimental work supporting the current invention, aversion of the Statistically Associating Fluid Theory (SAFT) EOS calledSAFT1 (Adidharma and Radosz, 1998) has been used for this purpose.Because phase separation experiments must be run at high temperaturesand pressures, it is usually impractical to sample individual phases inmulti-phase mixtures to determine their composition or physicalproperties, and thus the predicted properties of these phases have beenused in lieu of directly measured values in support of the currentinvention. This approach has been validated in other instances, wherematerial balances from pilot plants and commercial plants have been usedto validate SAFT1 EOS predictions. As an example, SAFT1 EOS models ofthe polymerization systems and liquid-liquid separation systemsdescribed in U.S. Pat. No. 6,881,800(B2) and U.S. Pat. No.7,163,989(B2), which include polymers, monomers, and catalysts similarto the current invention, but which include relatively large amounts ofalkane solvents in the polymerization medium, and are operated at lowerpressures than the current invention, have been verified by these typesof material balances.

Spinodal Decomposition:

Phase boundaries of mixtures, such as a polymerization medium, may bedepicted as T, P diagrams for a constant composition mixture asillustrated in FIG. 2, or alternatively, they may be depicted as T,cdiagrams for mixtures at constant pressure (as illustrated conceptuallyby the binodal curve in FIG. 28), or P,c diagrams for mixtures atconstant temperature, where the symbol c is used to denote composition.For multi-component mixtures the composition must be designated by aseries of composition variables c_(i), where i refers to each componentin the mixture, but for a binary mixture, a single variable c willadequately denote the composition. In general, the polymerization mediumof the current invention is a multi-component mixture, but for ourcurrent purposes of illustration, there is no generality lost byconsidering the polymerization medium to be a binary mixture of polymerand a single low molecular weight hydrocarbon, and the compositionvariable c can be taken to denote polymer concentration. If we take byway of example a phase boundary depicted by T,c at constant P asdepicted in FIG. 28, then the fluid-liquid phase boundary appears as acurve (which, following terminology commonly used in the art, we havedesignated as a binodal curve) where a minimum value of temperature(which is also commonly called the Lower Critical Solution Temperature,or LCST) exists at a concentration called the critical polymerconcentration (c_(crit)). This binodal curve, which represents thetwo-phase (fluid-liquid) phase boundary, is a locus of points where thesingle phase polymerization medium is in equilibrium with a two-phasemixture of monomer-rich and polymer-rich phases. From FIG. 28, it isapparent that for any given T & P, which is represented by horizontalline at T₁, there are two mixture compositions that are in equilibriumwith the Polymerization medium, and thus in equilibrium with each other.One of these mixture compositions is a monomer-rich composition, and theother a polymer-rich composition (these two compositions are designatedas c′ and c″ on FIG. 28). The bottom part of FIG. 28 illustrates a curverepresenting the chemical potential (Δμ_(1I)) of the binary mixture as afunction of c at a temperature equal to T₁ (note that a similar curvecould be constructed for all other values of T). Note also thatΔμ₁(c′)=Δμ₁(c″), since for two mixtures to be in equilibrium, theirchemical potentials must be equal. At other values of c on this curve,Δμ₁ assumes other values, since these other compositions are not inequilibrium with c′ and c″. Along this Δμ₁ curve, there are two otherspecial points, where the first partial derivative of Δμ₁ with respectto composition is zero (

Δμ₁/∂c=0). This is the thermodynamic criterium that defines the spinodalboundary, as is illustrated by the graphical construction in FIG. 28.For compositions on, or inside, the spinodal boundary, the compositionsof the monomer-rich and polymer-rich phases differ sufficiently fromequilibrium to form a thermodynamically unstable two-phase mixture,which tends to form a co-continuous morphology rather than a morphologywhere one of the two phases is dispersed as droplets in a continuum ofthe other phase. Inside the cross-hatched area in FIG. 28, the mixturetends to form a morphology where one of the two phases is dispersed in acontinuum of the other phase. When the polymer concentration in thepolymerization medium is higher than c_(crit), the polymer-rich phase iscontinuous, and when the polymer concentration in the polymerizationmedium is lower than c_(crit), the monomer-rich phase is continuous. Inmany embodiments of the current invention, the polymerization medium isa single phase fluid, such that its thermodynamic state (T,P,c) wouldplace it in the single phase region outside the binodal boundary on FIG.28. The process of spinodal decomposition refers to a process by which arapid change in the temperature or pressure is effected to move thethermodynamic state of the system across both the binodal and spinodalboundaries to a point inside the spinodal boundary. For this change tobe effective in producing the desired co-continuous morphology, the timethat the thermodynamic state of the system resides in the area betweenthe binodal and spinodal boundaries (cross-hatched area of FIG. 28) mustbe short enough that the undesired morphology does not have sufficienttime to become established. The exact value of time that satisfies thiscriterium must be determined empirically for each polymerization medium.Spinodal boundaries may also be depicted on phase diagrams which plot Pvs. T at constant composition, as illustrated in FIG. 29. A fulltreatment of this concept may be found in the paper “A Low-EnergySolvent Separation Method”, T. G. Gutowski et. al., Polymer Engineeringand Science, March 1983, v. 23, No. 4.

Dense fluids are defined as fluid media in their liquid or supercriticalstate with densities greater than 300 kg/m³.

Solid-fluid phase transition temperature is defined as the temperatureat and below which a solid polymer phase separates from thepolymer-containing fluid medium at a given pressure. The solid-fluidphase transition temperature can be determined by temperature reductionstarting from temperatures at which the polymer is fully dissolved inthe fluid reaction medium.

Solid-fluid phase transition pressure is defined as the pressure at andbelow which a solid polymer phase separates from the polymer-containingfluid medium at a given temperature. The solid-fluid phase transitionpressure can be determined by pressure reduction at constant temperaturestarting from pressures at which the polymer is fully dissolved in thefluid reaction medium.

A higher α-olefin or higher alpha-olefin is defined as an α-olefinhaving five or more carbon atoms.

The new numbering scheme for the Periodic Table Groups is used aspublished in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

The term “polymer” describes chain-like molecules synthesized from oneor more repeat units, or monomers, and is meant to encompasshomopolymers and copolymers, and includes any polymer having two or moredifferent monomers in the same chain, including random copolymers,statistical copolymers, interpolymers, and block copolymers.

Polymerization encompasses any polymerization reaction such ashomopolymerization and copolymerization. Copolymerization encompassesany polymerization reaction of two or more monomers.

When a polymer is referred to as comprising an olefin, the olefinpresent in the polymer is the polymerized form of the olefin. A“polyolefin” is a polymer comprising at least 50 mol % of one or moreolefins. Advantageously, a polyolefin comprises at least 60 mol %, or atleast 70 mol %, or at least 80 mol %, or at least 90 mol %, or at least95 mol %, or 100 mol % of one or more olefins, preferably 1-olefins,having carbon numbers of 2 to 20, preferably 2 to 16, or 2 to 10, or 2to 8, or 2 to 6.

A “high molecular weight” polymer has a Mw of 30 kg/mol or more.Advantageously, a high molecular weight polymer has a weight-averagedmolecular weight (Mw) of 50 kg/mol or more, or 75 kg/mol or more, or 100kg/mol or more, or 125 kg/mol or more, or 150 kg/mol or more.

An “oligomers” or “low molecular weight” polymer is a polymer having aMw of less than 30 kg/mol. Advantageously, oligomers have a Mw of lessthan 20 kg/mol, or less than 10 kg/mol, or less than 5 kg/mol, or lessthan 4 kg/mol, or less than 3 kg/mol, or less than 2 kg/mol, or lessthan 1 kg/mol. A “polyolefin oligomers” is a polyolefin that meets thedefinition of an oligomer.

A “high crystallinity” polymer has a heat of fusion (H_(f)) of greaterthan 70 J/g. Advantageously, a high crystallinity polymer has a H_(f) ofgreater than 80 J/g, or greater than 90 J/g, or greater than 100 J/g, orgreater than 110 J/g, or greater than 120 J/g.

A “low crystallinity” polymer has a H_(f) of 70 J/g or less.Advantageously, a low crystallinity polymer has a H_(f) of 60 J/g orless, or 50 J/g or less, or 40 J/g or less, or 30 J/g or less, or 20 J/gor less, or 10 J/g or less, or 5 J/g or less, or an H_(f) that is toosmall to measure reliably.

A “base polymer” or “base resin” is a polyolefin or polyolefin blend theproperties of which are modified by blending them with one or moreplasticizers. Typically, a base polymer is a high crystallinity, highmolecular weight polyolefin.

A “soft” polymer is a low crystallinity high molecular weight polymer.Typically, a soft polymer has a glass transition temperature (Tg) ofless than 0° C. Preferably, a soft polymer has a Tg of less than −10°C., or less than −20° C., or less than −30° C., or less than −40° C. A“soft polyolefin” is a polyolefin that meets the definition of a softpolymer. Examples of soft polyolefins include “plastomers” whichcomprise a majority of ethylene (ethylene plastomers) or a majority ofpropylene (propylene plastomers) with crystallizable sequences of themajority monomer, and “elastomers” which have a Mw of 100 kg/mol or more(such as EP elastomers which comprise ethylene, propylene, andoptionally one or more dienes).

Plasticizers are defined as per J. K. Sears, J. R. Darby, THE TECHNOLOGYOF PLASTICIZERS, Wiley, New, York, 1982, stating that “Plasticizer is amaterial incorporated in a plastic to increase its workability and itsflexibility or distensibility (elongation). Addition of the plasticizermay lower the melt viscosity, temperature or the second-ordertransition, or the elastic modulus of the plastic.” Plasticizers have alower glass transition temperature and/or lower modulus and/or lowercrystallinity and/or lower Mw than the base polymer. They may beoligomers, soft polymers, or other fluids.

A series reactor cascade includes two or more reactors connected inseries, in which the effluent of an upstream reactor is fed to the nextreactor downstream in the reactor cascade. Besides the effluent of theupstream reactor(s), the feed of any reactor can be augmented with anycombination of additional monomer, catalyst, scavenger, or solvent freshor recycled feed streams.

Reactor train or reactor branch or reactor leg refers to apolymerization reactor or to a group of polymerization reactors of thein-line blending process disclosed herein that produces a single blendcomponent. If the reactor train contains more than one reactor, thereactors are arranged in a series configuration within the train. Theneed for having more than one reactor in a reactor train may, forexample, arise when an in-line blend component cannot be produced at thedesired rate economically in a single reactor but there could be alsoreasons related to blend component quality, such as molecular weight orcomposition distribution, etc. Since a reactor train can comprisemultiple reactors and/or reactor zones in series, the single blendcomponent produced in a reactor train may itself be a polymer blend ofpolymeric components with varying molecular weights and/or compositions.However, in order to simplify the description of different embodimentsof the in-line blending processes disclosed herein, the polymericproduct of a reactor train is referred to simply as blend component orpolymeric blend or plasticizer blend component regardless of itsmolecular weight and/or compositional dispersion. For the purpose ofdefining the process of the present invention, parallel reactors will bealways considered as separate reactor trains even if they produceessentially the same in-line blend component. Also, spatially separated,parallel reaction zones that do not exchange or mix reaction mixturesby, for example, pump-around loops, or by other recirculation methods,will be considered as separate parallel reactor trains even when thoseparallel zones are present in a common shell and fall within the in-lineblending process disclosed herein.

Reactor bank refers to the combination of all polymerization reactors inthe polymerization section of the in-line polymer blending processdisclosed herein.

A parallel reactor configuration includes two or more reactors orreactor trains connected (also referred to as fluidly connected) inparallel. A reactor train, branch, or leg may include one reactor oralternatively more than one reactor configured in a seriesconfiguration. For example, a reactor train may include two, or three,or four, or more reactors in series. The entire parallel reactorconfiguration of the polymerization process disclosed herein, i.e., thecombination of all parallel polymerization reactor trains forms thereactor bank.

Monomer recycle ratio refers to the ratio of the amount of recycledmonomer fed to the reactor divided by the total (fresh plus recycled)amount of monomer fed to the reactor.

Polymerization system is defined to be monomer(s) plus optionalcomonomer/s) plus polymer(s) plus optional inert solvent(s)/diluent(s)plus optional scavenger(s). Note that for the sake of convenience andclarity, the catalyst system is always addressed separately in thepresent discussion from other components present in a polymerizationreactor. In this regard, the polymerization system is defined herenarrower than customary in the art of polymerization that typicallyconsiders the catalyst system as part of the polymerization system. Bythe current definition, the mixture present in the polymerizationreactor and in its effluent is composed of the polymerization systemplus the catalyst system. Dense fluid polymerization systems havegreater than 300 kg/m³ fluid phase density, all of their componentslisted above, i.e., the monomer(s) plus optional comonomer(s) pluspolymer(s) plus optional inert solvent(s)/diluent(s) plus optionalscavenger(s), are in fluid state, or stating differently, none of theircomponents is in solid state. Note that these qualifications, may bedifferent for the catalyst system since it is not part of thepolymerization system.

A homogeneous polymerization system contains all of its componentsdispersed and mixed on a molecular scale. In our discussions,homogeneous polymerization systems are meant to be in their dense fluid(liquid or supercritical) state. Note that our definition of thepolymerization system does not include the catalyst system, thus thecatalyst system may or may not be homogeneously dissolved in thepolymerization system. A homogeneous system may have regions withconcentration gradients, but there would be no sudden, discontinuouschanges of composition on a micrometer scale within the system. Inpractical terms, a homogeneous polymerization system has all of itscomponents in a single dense fluid phase. Apparently, a polymerizationsystem is not homogeneous when it is partitioned to more than one fluidphase or to a fluid and a solid phase. The homogeneous fluid state ofthe polymerization system is represented by the single fluid region inits phase diagram.

A homogeneous polymerization process operates with a homogeneouspolymerization system. Note that the catalyst system is not part of thepolymerization system, thus it is not necessarily dissolvedhomogeneously in the polymerization system. A reactor in which ahomogeneous polymerization process is carried out will be referred to ashomogeneous polymerization reactor.

The following abbreviations are used: Me is methyl, Ph is phenyl, Et isethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu isbutyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiarybutyl, TMS is trimethylsilyl, TIBA is tri-isobutylaluminum, MAO ismethylaluminoxane, pMe is para-methyl, flu is fluorenyl, cp iscyclopentadienyl.

By continuous is meant a system that operates (or is intended tooperate) without interruption or cessation. For example, a continuousprocess to produce a polymer would be one where the reactants arecontinually introduced into one or more reactors and polymer product iscontinually withdrawn.

Slurry polymerization refers to a polymerization process in whichparticulate, solid polymer (e.g., granular) forms in a dense fluid or ina liquid/vapor polymerization medium. The dense fluid polymerizationmedium can form a single or two fluid phases, such as liquid,supercritical fluid, or liquid/liquid, or supercriticalfluid/supercritical fluid, polymerization medium. In the liquid/vaporpolymerization medium, the polymer resides in the liquid (dense) phase.

Solution polymerization refers to a polymerization process in which thepolymer is dissolved in a liquid polymerization system in which thesolvent for the polymeric product is an inert solvent(s) or themonomer(s) or their blends. Solution polymerization comprises a liquidpolymerization system. Solution polymerization may be performed atconditions where a vapor and a liquid phase are present, in which casethe polymerization system comprises the liquid phase. Advantageously,solution polymerization is performed with liquid-filled reactors, in thesubstantial absence of a vapor phase. Liquid-filled reactor operationsare characterized by reactor pressures that are at or above the bubblepoint of the polymerization system. Bubble point is defined as thepressure at which a liquid starts forming vapor bubbles at a giventemperature. Bubble point pressures of hydrocarbon blends can be readilydetermined by standard techniques known in the art of chemicalengineering. Methods suitable for conducting such calculations areequation of state methods, such as Peng Robinson or Suave Redlich Kwong.Bubble point of liquids can be also readily measured by methods such asdisclosed in T. Tsuji et al., Fluid Phase Equilibria 219 (2004) 87-92 orin R. W. et al., U.S. Pat. No. 6,223,588 (2001). The bubble point of aliquid can be conveniently determined by reducing the pressure atconstant temperature of a compressed fluid until the first vapor bubbleis formed. Solution polymerization typically performed in a singlehomogeneous liquid phase, but solution polymerization comprising twoliquid phases are also known. In the latter case, the polymerizationsystem is below of its cloud point pressure but above of its solid-fluidphase transition pressure and temperature. In these two-phase liquidpolymerizations systems, the polymerization system is typicallypartitioned into two liquid phases, a polymer-lean and a polymer-richliquid phase. In a well-stirred polymerization reactor, these two phasesare finely dispersed. Note, however, that these two-phase liquidpolymerizations systems have none of their components in solid state.

Supercritical polymerization refers to a polymerization process in whichthe polymerization system is in its dense supercritical state, i.e. whenthe density of the polymerization system is above 300 g/L and itstemperature and pressure are above the corresponding critical values.Supercritical polymerization is typically performed in a singlehomogeneous supercritical phase, but supercritical polymerizationcomprising two supercritical fluid phases is also contemplated. In thelatter case, the polymerization system is below of its cloud pointpressure but above of its solid-fluid phase transition pressure andtemperature. In these two-phase supercritical fluid polymerizationssystems, the polymerization system is typically partitioned into twofluid phases, a polymer-lean and a polymer-rich fluid phase. In awell-stirred polymerization reactor, these two phases are finelydispersed. Note, however, that these two-phase supercritical fluidpolymerizations systems have none of their components in solid state.

Bulk polymerization refers to a polymerization process in which thedense fluid polymerization system contains less than 40 wt %, or lessthan 30 wt %, or less than 20 wt %, or less than 10 wt %, or less than 5wt %, or less than 1 wt % of inert solvent or diluent. The productpolymer may be dissolved in the dense fluid polymerization system or mayform a solid phase. In this terminology, slurry polymerization, in whichsolid polymer particulates form in a dense fluid polymerization systemcontaining less than 40 wt % of inert solvent or diluent, will bereferred to as a bulk slurry polymerization process or bulkheterogeneous polymerization process. The polymerization process inwhich the polymeric product is dissolved in a single-hase dense fluidpolymerization system containing less than 40 wt % of inert solvent ordiluent will be referred to as bulk homogeneous polymerization process.The polymerization process in which the polymeric product is dissolvedin a liquid polymerization system containing less than 40 wt %, or lessthan 30 wt %, or less than 20 wt %, or less than 10 wt %, or less than 5wt %, or less than 1 wt % of inert solvent or diluent will be referredto as bulk solution polymerization process. The polymerization processin which the polymeric product is dissolved in a single-phasesupercritical polymerization system containing less than 40 wt %, orless than 30 wt %, or less than 20 wt %, or less than 10 wt %, or lessthan 5 wt %, or less than 1 wt % of inert solvent or diluent will bereferred to as bulk homogeneous supercritical polymerization process.

Homogeneous supercritical polymerization refers to a polymerizationprocess in which the polymer is dissolved in a single-phase densesupercritical fluid polymerization medium, such as an inert solvent ormonomer or their blends in their supercritical state. As describedabove, when the supercritical fluid polymerization system contains lessthan 40 wt %, or less than 30 wt %, or less than 20 wt %, or less than10 wt %, or less than 5 wt %, or less than 1 wt % of inert solvent andthe polymer is dissolved in the dense supercritical fluid, the processis referred to as a bulk homogeneous supercritical polymerizationprocess. Homogeneous supercritical polymerization should bedistinguished from heterogeneous supercritical polymerizations, such asfor example, supercritical slurry processes, the latter of which areperformed in supercritical fluids but form solid polymer particulates inthe polymerization reactor. Similarly, bulk homogeneous supercriticalpolymerization should be distinguished from bulk solutionpolymerization, the latter of which is performed in a liquid as opposedto in a supercritical polymerization system.

Single-pass conversion of monomer i in reactor train j is defined by thefollowing formula: Single pass conversion of monomer i in reactor trainj (%)=100×[(reactor train j effluent flow rate in weight perhour)×(polymer product concentration in the effluent of reactor train jin weight fraction)×(monomer i concentration in the polymer product madein reactor train j in weight fraction)]/[(reactor train j feed flowrate, including fresh and recycled, in weight per hour)×(monomer iconcentration in the feed of reactor train j, including fresh andrecycled, in weight fraction)].

Overall conversion of monomer i in reactor train j is defined by thefollowing formula: Overall conversion of monomer i in reactor train j(%)=100×[(reactor train j effluent flow rate in weight perhour)×(polymer product concentration in the effluent of reactor train jin weight fraction)×(monomer i concentration in the polymer product madein reactor train j in weight fraction)]/[(reactor train j fresh feedflow rate, excluding recycled, in weight per hour)×(monomer iconcentration in the fresh feed of reactor train j, excluding recycled,in weight fraction)].

The total monomer feed rate of a given train is equal to the sum offresh (make up) monomer feed rate plus recycled monomer feed rate inweight per hour.

The flow (feed, effluent, recycle, purge etc. flow) rate of monomercomponent i in weight per hour is equal to the total flow (feed,effluent, recycle, purge etc. flow) rate in weight per hour multipliedby the weight fraction of monomer component i.

Conversion rate of monomer i in reactor train j expressed in weight perhour is equal to [(reactor train j effluent flow rate in weight perhour)×(polymer product concentration in the effluent of reactor train jin weight fraction)×(monomer i concentration in the polymer product madein reactor train j in a single pass in weight fraction)].

Unreduced reactor effluent refers to the whole effluent stream emergingfrom a reactor train, leg, or branch that has yet to undergo phaseseparation in one or more high pressure separators, i.e., it containsthe entire unreduced polymerization system as it emerges from thereactor train, leg, or branch. As opposed to unreduced reactoreffluents, reduced reactor effluents are the polymer-containing streamsderived from the unreduced reactor effluents. Reduced reactor effluentscontain less than the entire, unreduced polymerization system as itemerges from the reactor train, leg, or branch. In practical terms,reduced effluents are formed by separating and removing a part of themonomer and the optional inert solvent/diluent content in the form of amonomer-rich stream. In the practice of the present disclosure, theseparation of the said monomer-rich effluent and thus the reduction ofthe unreduced reactor effluent is performed by phase separation thatgenerates the said monomer-rich stream and the said reduced reactoreffluent, the latter of which in the form of a polymer-enriched stream.Stating it yet another way, the unreduced reactor effluent is the wholereactor effluent before any split of that effluent occurs, while areduced effluent is formed after at least one split in which some of thelight components (monomers and the optional inert solvents/diluents) areremoved from the whole, unreduced reactor effluent.

Base polymers, base polymer components or base resins are polyolefinsthe properties of which are modified by blending them with one or moreplasticizers and optionally other additives, such as waxes,antioxidants, nucleating and clarifying agents, slip agents, flameretardants, heat and UV stabilizers, antiblocking agents, fillers,reinforcing fibers, antistatic agents, lubricating agents, coloringagents, foaming agents, etc.

An in-line blending process disclosed herein refers to one where thepolymerization and the polymer blending processes are integrated in asingle process and at least one of the polymerization trains operatesunder solution or homogeneous supercritical conditions. Although in-lineblending processes typically employ polymerization trains using solutionor homogeneous supercritical polymerization systems, one or more of thepolymerization trains may employ slurry polymerization systems,particularly bulk slurry polymerization systems. When the polymerizationbank includes one or more slurry polymerization trains, the effluents ofthose slurry trains are always heated above their solid-fluid transitionpoints and optionally pressurized before mixing them with the effluentsof other trains to enable fluid-phase mixing.

In-line polymer blend or in-line blend disclosed herein refers to amixture of two or more polymeric components, at least one of which isproduced under either homogeneous supercritical polymerizationconditions or homogeneous solution polymerization conditions. The saidpolymeric in-line blend components are produced internally in thein-line blending process and are mixed in the same process withoutrecovering them in their solid state, i.e., the polymeric in-line blendcomponents are produced and blended in-line. Optionally, the in-lineblends may also contain common polymer additives which are used toimpart certain desirable properties and are produced outside theinvention process, such as UV stabilizers, antioxidants, nucleatingagents, cross-linking agents, fillers, etc. Such additives are describedin PLASTICS ADDITIVE HANDBOOK, 5th Ed.; H. Zweifel, Ed. (Hanser-Gardner,2001) and may be present at any effective concentration but typically atless than 10 wt %, or even less than 1 wt %, by weight. The in-lineblends may also contain polymeric additives/modifiers produced outsidethe invention process (i.e. off-line). They are typically added in minoramounts, i.e., less than 50 wt %, or less than 40 wt %, or less than 30wt %, or less than 20 wt %, or less than 10 wt %, or less than 5 wt %,or less than 1 wt % by weight. These optional additives mayadvantageously be blended in-line, i.e., before the plasticizer-polymerblend is recovered in their solid state, such as in the finishingequipment that converts the molten polymer-plasticizer blend intoformulated granules, pellets, bales, or the like.

In-line polymer-plasticizer blend, or in-line-plasticized polymer orin-line-plasticized polymer blend disclosed herein refers to a mixtureof one or more polymeric components (base polymer) with one or moreplasticizers, wherein at least one of the polymeric components of thebase polymer is produced in-line (i.e., in one or more of the reactortrains of the disclosed in-line blending processes) under eithersupercritical polymerization conditions or solution polymerizationconditions and the one or more plasticizer components are blended withthe base polymer also in-line, i.e., before the base polymer isrecovered in its essentially pure, solid form. The one or moreplasticizers blended in-line with the base polymer may be producedin-line, i.e., in one of the reactor trains of the reactor bank of thedisclosed processes, or may be produced in a separate plant and added toa stream comprising the base polymer or a combination thereof. When noneof the plasticizers comprising the in-line-plasticized polymer orin-line-plasticized polymer blend are produced in-line, the base polymeris an in-line polymer blend of two or more polymer components. When oneor more plasticizer components are produced in-line, the base polymermay be either a single component or an in-line blend of two or morepolymer components. Note that the one or more polymeric componentsconstituting the base polymer are produced and mixed internally in thedisclosed in-line blending processes. Furthermore, the disclosedblending processes blend the plasticizers and the base polymer in-line,i.e., before the base polymer is recovered in its essentially pure,solid form. Finally, note that the base polymer may itself be an in-lineblend of polymers or alternatively may be a single polymer component. Inthe latter case, one or more of the plasticizer components of thein-line-plasticized polymer are also produced in-line. The blendingpoint for combining the polymer- and plasticizer-containing streams maybe anywhere downstream of the reactor bank of the disclosed in-linepolymer blending processes. Advantageously, the one or more plasticizersare blended with a base polymer containing stream that still contains atleast some of the low molecular weight components, such as the monomersand the optional inert solvents/diluents of the polymerization system,to facilitate the blending process by the virtue of reduced viscosity.The said advantageous mixing points of the disclosed in-line blendingprocesses exist downstream of the reactors and upstream of the extruderor devolatizing extruder of the product finishing section of theprocesses disclosed herein, particularly, downstream of the reactors andupstream of or in the low-pressure separator deployed just before thesaid extruder or devolatizing extruder of the finishing section.

The term plasticized polyolefin masterbatch, or plasticized polymermasterbatch, is defined as a blend of one or more high molecular weightbase polymer(s) and one or more plasticizer(s) made primarily forfurther compounding, i.e., for further blending with high molecularweight polymer to produce plasticized polymeric product. The purpose ofmaking plasticized masterbatches essentially is to deliver plasticizersin a pelletized form and thus enable compounding in the traditionalcompounding facilities equipped to handle pelletized polymers buttypically not equipped to handle fluids and or bales. Pelletization isafforded by blending one or more high molecular weight base polymer withone or more plasticizers, wherein the base polymer creates a matrixproviding for proper processability and pellet stability. Masterbatchestypically have high concentration of plasticizers for efficient deliveryof the plasticizer package. The compounders blend these masterbatches inappropriate ratios with additional amounts of base polymers to adjusttheir properties for final use. When the plasticized polyolefinmasterbatch is made in-line, i.e., when the plasticizer is blended withthe base polymer in-line, the plasticized masterbatch is also referredto as in-line-plasticized polyolefin masterbatch, or in-line-plasticizedpolymer masterbatch.

The term mineral oil includes any fluid derived from petroleum crude oilthat has been subjected to refining steps (such as distillation, solventprocessing, hydroprocessing, and/or dewaxing). This also includespetroleum-based oils that are extensively purified and/or modifiedthrough severe processing treatments. It excludes synthetic oils, whichhave been manufactured by combining monomer units using catalysts and/orheat. In the polymer processing art, mineral oils are often calledprocess oils, extender oils, white oils, technical oils, or food gradeoils. Such fluids typically have a viscosity index less than 120, mosthave a viscosity index less than 110, and many have a viscosity index of100 or less.

The American Petroleum Institute categorizes mineral oils as Group I,II, or III basestocks based upon saturates content, sulfur content, andViscosity Index (VI). Group I basestocks are solvent-refined mineraloils. They contain the most unsaturates and sulfur of the three groups,and have the lowest viscosity indices. Group II and Group III basestocksare hydroprocessed mineral oils. The Group III basestocks contain lessunsaturates, less sulfur, and have higher VIs compared to Group IIbasestocks. Even in cases where a mineral oil is not identified by anAPI Group classification, it is still possible, for purposes of thisinvention, to define two classes of mineral oils based on ViscosityIndex: “Group I/II mineral oils” which have VI less than 120; and “GroupIII mineral oils” which have VI of 120 or more.

As used herein, the following terms have the indicated meanings:“naphthenic” describes cyclic (mono-ring and/or multi-ring) saturatedhydrocarbons (i.e., cycloparaffins) and branched cyclic saturatedhydrocarbons; “aromatic” describes cyclic (mono-ring and/or multi-ring)unsaturated hydrocarbons and branched cyclic unsaturated hydrocarbons asdescribed in J. March, ADVANCED ORGANIC CHEMISTRY Fourth ed., Wiley, NewYork, 1992; “hydroisomerized” describes a catalytic process in whichnormal paraffins and/or slightly branched isoparaffins are converted byrearrangement into more branched isoparaffins (also known as“isodewaxing”); “wax” is a hydrocarbonaceous material existing as asolid at or near room temperature, with a melting point of 0° C. orabove, and consisting predominantly of paraffinic molecules, most ofwhich are normal paraffins; “slack wax” is the wax recovered frompetroleum oils such as by solvent dewaxing, and may be furtherhydrotreated to remove heteroatoms.

The term paraffin includes all isomers such as normal paraffins(n-paraffins), branched paraffins, isoparaffins, cycloparaffins, and mayinclude cyclic aliphatic species, and blends thereof.

The term isoparaffin means that the paraffin chains possess C₁ to C₁₈(more commonly C₁ to C₁₀) alkyl branching along at least a portion ofeach paraffin chain, and may include cycloparaffins with branched sidechains as a minor component (advantageously less than 30%, or less than20%, or less than 10%, or 0% of carbons are in cycloparaffinsstructures). More particularly, isoparaffins are saturated aliphatichydrocarbons whose molecules have at least one carbon atom bonded to atleast three other carbon atoms or at least one side chain (i.e., amolecule having one or more tertiary or quaternary carbon atoms);various isomers of each carbon number (i.e. structural isomers) willtypically be present. Isoparaffins with multiple alkyl branches mayinclude any combination of regio and stereo placement of those branches.

By heterogeneous composition is meant a composition having two or moremorphological phases. For example a blend of two polymers where onepolymer forms discrete domains dispersed in a matrix of another polymeris said to be heterogeneous in the solid state. Heterogeneous blendsalso include co-continuous blends where the blend components areseparately visible, but it is unclear which is the continuous phase andwhich is the discontinuous phase. Such heterogeniety in the compositionand mophology of the blend occurs in phase of dimensions of 100 μm toless than 0.1 μm, as determined using optical microscopy, scanningelectron microscopy (SEM), atomic force microscopy (AFM), or in somecases by dynamic mechanical thermal analysis (DMTA); in the event thereis disagreement among the methods, then the SEM data shall be used. Bycontinuous phase is meant the matrix phase in a heterogeneous blend. Bydiscontinuous phase is meant the dispersed phase in a heterogeneousblend.

By homogeneous composition is meant a composition having substantiallyone morphological phase in the same state. For example, a blend of twopolymers where one polymer is miscible with another polymer is said tobe homogeneous in the solid state. Such morphology is determined usingoptical microscopy, SEM, AFM, or in some cases by DMTA; in the eventthere is disagreement among the methods, then the SEM data shall beused.

Unless noted otherwise:

Percents express a weight percent (wt %), based on the total amount ofthe material or component at issue;

Physical and chemical properties described are measured using thefollowing test methods:

Kinematic Viscosity (KV) ASTM D 445 Viscosity Index (VI) ASTM D 2270Pour Point ASTM D 97 Specific Gravity and Density ASTM D 4052(15.6/15.6° C.) Flash Point ASTM D 92 Distillation range, initialboiling ASTM D 86 point, and final boiling point Glass TransitionTemperature ASTM E 1356 (10° C./min, midpoint (T_(g)) convention)Saturates Content ASTM D 2007 Sulfur Content ASTM D 2622 Melt Index (MI)ASTM D 1238 (190° C./2.16 kg) Melt Flow Rate (MFR) ASTM D 1238 (230°C./2.16 kg) Mooney Viscosity ASTM D 1646 Density ASTM D 4052 InjectionMolding ASTM D 4101 DMTA Properties ASTM D 4065 Tensile Properties ASTMD 638 (Type I bar, 5 cm/min) 1% Secant Flexural Modulus ASTM D 790 (A,1.3 mm/min) Heat Deflection Temperature ASTM D 648 (0.45 MPa) VicatSoftening Temperature ASTM D 1525 (200 g) Gardner Impact Strength ASTM D5420 (GC) Notched Izod (NI) Impact ASTM D 256 (Method A, or StrengthMethod E if “reverse notch” noted, RNI) Notched Charpy Impact StrengthASTM D 6110 Multi-Axial Impact Strength ASTM D 3763 (15 MPH) Shore(Durometer) Hardness ASTM D 2240 (A or D, 15 sec delay)

For polymers and oligomers have a KV100° C. of greater than 10 cSt, theweight-averaged molecular weight (Mw), number-averaged molecular weight(Mn), and z-averaged molecular weight (Mz) are each determined utilizinggel permeation chromatography (GPC) based on calibration usingpolystyrene standards; Mn for oligomers having a KV100° C. of 10 cSt orless is determined by gas chromatography with a mass spectrometerdetector;

Branched Paraffin to n-paraffin ratio, % mono-methyl species, and % sidechains with X number of carbons are determined by ¹³C-NMR;

Composition Distribution Breadth Index (CDBI) is a measure of thecomposition distribution of monomer within the polymer chains and ismeasured by the procedure described in PCT publication WO 93/03093,published Feb. 18, 1993 including that fractions having a weight averagemolecular weight (Mw) below 15,000 are ignored when determining CDBI.For purposes of this invention a homopolymer is defined to have a CDBIof 100%.

Heat of fusion, H_(f), is measured between the temperatures of 21 and230° C. by differential scanning calorimetry (DSC) second melt;

Molecular weight distribution (MWD) is defined as the weightaveragemolecular weight divided by the numberaverage molecular weight (Mw/Mn);and

When melting or crystallization point is referred to and there is arange of melting or crystallization temperatures, the melting orcrystallization point is defined to be the peak melting orcrystallization temperature from a DSC trace, and, unless notedotherwise, when there is more than one melting or crystallization peak,it refers to the peak melting or crystallization temperature for thelargest peak among principal and secondary melting peaks, as opposed tothe peak occurring at the highest temperature, thereby reflecting thelargest contribution to the calorimetric response of the material.

DETAILED DESCRIPTION

As disclosed in U.S. Patent Application No. 60/876,193 filed on Dec. 20,2006, herein incorporated by reference in its entirety, an improvedin-line process for blending polymers has been developed to improveblend quality and reduce the capital and operating costs associated witha combined polymerization and blending plant. The present disclosureexpands the scope of U.S. Patent Application No. 60/876,193 to anin-line blending process with two or more parallel reactor trains forproducing plasticized polyolefins, plasticized polyolefin blends, andplasticized polyolefin masterbatches. These plasticized polyolefinproducts are also referred to herein as plasticized polymers, orplasticized polymer blends, or plasticized polymer masterbatches, orin-line-plasticized polyolefins/polymers or in-line-plasticizedpolyolefin/polymer blends, or plasticized polyolefin/polymermasterbatches.

Disclosed herein are novel in-line blending processes for producingplasticized polymers in polymerization processes in which at least oneof the reactor trains, advantageously each reactor train, operates witha fluid phase, advantageously with a homogeneous fluid phase (i.e., witha homogeneous liquid phase or homogeneous supercritical phase)polymerization system and the polymerization system in at least one ofthe polymerization reactor trains includes an olefin monomer that hastwo or more carbon atoms. More particularly, the present disclosure isrelated to making in-line-plasticized polymers or in-line-plasticizedpolymer blends when one or more of the blending components is a suitableplasticizer, such as, for example, oligomers, polymers, and copolymersof C₅ to C₂₀ alpha olefins and mixtures thereof (also calledpoly(alpha-olefin)s) or PAOs), oligomers and copolymers of ethylene andpropylene, oligomers and copolymers of ethylene and C₄-C₂₀ olefins,oligomers and copolymers of propylene and C₄-C₂₀ olefins, paraffin oilsand waxes, mineral oils, synthetic oils, synthetic and mineral lube basestocks, elastomers, plastomers, etc., acting as a plasticizer within ahigh molecular weight polyolefin base resin (also referred to as basepolymer). The plasticizer components may be made within the same plantor may be produced off-line or combination thereof and blended in-linebefore the high molecular weight polyolefin base polymer component isrecovered in its essentially pure solid state. The blending point forcombining the polymer- and plasticizer-containing streams may beanywhere downstream of the reactor bank of the disclosed in-line polymerblending processes. Advantageously, the one or more plasticizers areblended with a base polymer containing stream that still contains atleast some of the low molecular weight components, such as the monomersand the optional inert solvents/diluents of the polymerization system,to facilitate the blending process by the virtue of reduced viscosity.The said advantageous mixing points of the disclosed in-line blendingprocesses exist downstream of the reactors and upstream of the extruderor devolatizing extruder of the product finishing section of theprocesses disclosed herein, particularly, downstream of the reactors andupstream of or in the low-pressure separator deployed just before thesaid extruder or devolatizing extruder of the finishing section, whichis also referred to as the separator section of the disclosed processes.All embodiments of the disclosed processes blend the plasticizers andthe base polymer (the latter may be a polymer blend itself) in-line inthe separator section of the in-line blending process, i.e., before thebase polymer is recovered in its essentially pure, solid form. Thepolyolefin-plasticizer-rich phase from the separator section of thein-line blending process is then conveyed to a downstream finishingstage for further monomer stripping, drying and/or pelletizing to formthe plasticized polyolefin blend product of the in-line blendingprocess. Plasticized polyolefin blends may be made cheaper, easier, andwith improved mixing if the high molecular weight polyolefin componentis present in a solution state and blended with a plasticizer also in asolution state. For example, when a supercritical polymerization processis employed to produce the base polyolefin, the blending may beperformed in the production plant before the supercritical monomeracting as solvent is removed and the high molecular weight base resin isrecovered.

In some embodiments of the disclosed processes, the one or morepolyolefin effluent streams from the one or more parallel base polymerreactor trains and the plasticizer feed streams (produced either in-lineor off-line or combination thereof) are combined downstream of thereactor bank and upstream of or in a high-pressure phase separator thatsimultaneously provides blending of the in-line blend components andseparation of the monomer(s) and inert diluents(s) or solvents(s) fromthe base polyolefin blend component(s) and plasticizer blendcomponent(s) by bringing the combined reactor effluent and plasticizerfeed streams below the cloud point of the mixture while maintaining saidmixed streams above the solid-fluid phase transition point by adjustingthe temperature and pressure of the effluent streams individually (i.e.,before the mixing point), or combined (i.e., after the mixing point);when the reactor effluents are combined upstream of a phase separator,optionally passing the mixed reactor effluent streams through one ormore static mixers before entering the said separator to enhance mixing;maintaining the pressure within the separator vessel below the cloudpoint pressure to form two fluid phases comprising apolyolefin-plasticizer-rich fluid phase and a monomer-rich fluid phase;maintaining the temperature in the separator above the solid-fluid phasetransition temperature to allow the settling to the bottom and theformation of a continuous layer at the bottom of a denser well-mixedfluid polyolefin-plasticizer-rich blend phase and allowing the rising tothe top and the formation of a continuous layer of a lower-densitymonomer-solvent-rich phase at the top; separating a monomer-rich phasefrom a polyolefin-plasticizer-rich blend phase and recycling theseparated monomer-rich phase directly or after further treatment to thepolymerization trains; optionally, further reducing the pressure of thesaid first polyolefin-plasticizer-rich blend phase upstream of or in alow-pressure separator to achieve another fluid-fluid separation into amore concentrated polyolefin-plasticizer-rich fluid phase and anothermonomer-rich phase while maintaining the temperature above thesolid-fluid phase transition temperature by optionally further heatingthe first polyolefin-plasticizer rich blend stream; optionally, addingcatalyst killer(s), and/or polymer modifier(s) and/or additive(s) intheir dense fluid state (i.e., liquid, supercritical fluid, molten, ordissolved state) to the base polyolefin- and/or plasticizer-containingeffluent stream(s) at any desired point downstream of the first pressureletdown valves in any of the individual or combined effluent streams ofthe reactor trains in the reactor bank of the disclosed processes. Thepolyolefin-plasticizer-rich phase from the separator section of thein-line blending process is then conveyed to a downstream finishingstage for further monomer stripping, drying and/or pelletizing to formthe plasticized polyolefin blend product of the in-line blendingprocess.

Another embodiment of the novel in-line blending processes forplasticized polyolefins includes providing two or more reactor trainsconfigured in parallel wherein one or more of the reactor trains produceone or more high molecular weight polyolefins (base polymers) and one ormore of the reactor trains produce one or more plasticizers. For the oneor more parallel reactor trains producing the one or more high molecularweight polyolefins, the process includes contacting olefin monomer(s)with catalyst systems, optional comonomer(s), optional scavenger(s), andoptional diluent(s) or solvent(s). At least one of the said parallelreactor trains producing the one or more high molecular weightpolyolefins, and advantageously each of them, operates at a temperatureabove the solid-fluid phase transition temperature of the polymerizationsystem and at a pressure no lower than the solid-fluid phase transitionpressure and no lower than 10 MPa below, or no lower than 5 MPa below,or no lower than 1 MPa below, or no lower than 0.1 MPa below, or nolower than 0.01 MPa below the cloud point pressure of the polymerizationsystem and less than 1500 MPa, particularly between 1 and 300 MPa, stillmore particularly between 1 and 250 MPa, wherein the polymerizationsystem comprises the monomer, any comonomer(s), any scavenger(s), anydiluent(s) or solvent(s) present, and the polyolefin-based polymerproduct and where the catalyst system comprises catalyst precursorcompound(s), activator(s), and optional support(s); and forming apolyolefin/polymer reactor effluent stream including a polyolefin blendcomponent (base polymer blend component) dissolved in the effluent densefluid polymerization system. For the one or more of the reactor paralleltrains producing a plasticizer, the process includes contacting olefinmonomer(s) with catalyst systems, optional comonomer(s), optionalscavenger(s), and optional diluent(s) or solvent(s) at an effectivereactor temperature and pressure of the plasticizer system to create aplasticizer, wherein the plasticizer system comprises the monomer, anycomonomer(s), any scavenger(s), any diluent(s) or solvent(s) present,and the plasticizer product and where the catalyst system comprisescatalyst precursor compound(s), activator(s), and optional support(s);and forming a plasticizer reactor effluent stream including aplasticizer blend component dissolved in the monomer and optionaldiluent(s) or solvent(s). Note that other aspects of the blending andseparation methods and the location of advantageous blending points arenot effected, and thus are the same as in other embodiments.

In some other embodiments, one or more plasticizers produced in-line,i.e., in one or more reactor trains of the disclosed processes, arefully recovered before blending them with the one or more effluentstreams comprising the one or more high molecular weight polymercomponents of the base polymer. By fully recover, we mean to recoverthem in their essentially pure, solvent- and monomer-free, liquid form.Fully recovering in-line-produced plasticizer fluids before blendingthem with the base polymer containing streams is particularlyadvantageous when the combined monomer pool of the one or moreplasticizer trains producing plasticizer fluids has monomer members thatare not part of the combined monomer pool of the one or more polymertrains producing the base polymer due to reduced complexity and thusreduced cost of monomer recycle. Such separate recovery of the monomersand optional solvents of the one or more plasticizer trains may allowthe direct recycle of the plasticizer monomers to the one or moreplasticizer reactor trains. Since many plasticizers have relatively lowviscosity at the blending conditions even in the absence of lowmolecular weight diluents, such as monomers and optional solventspresent in the plasticizer reactor train effluents, they can be blendedwith the effluent streams comprising the high molecular weight polymercomponents without negatively impacting the efficiency of the blendingprocess. Such full recovery may not be always advantageous, particularlyfor plasticizers with high viscosity at the blending conditions, such asin the case of some plastomers and elastomers. As for any embodimentwith in-line produced plasticizers, these embodiments may optionallyalso employ off-line-produced plasticizers after proper conditioning,i.e., after bringing them into fluid phase by dissolving them in aproper solvent or by melting them. Note that other aspects of theblending and separation methods and the location of advantageousblending points are not effected, and thus are the same as in otherembodiments employing only off-line-produced plasticizers or as inembodiments that do not fully recover any of the in-line-producedplasticizers.

Yet another embodiment of the novel in-line blending processes forplasticized polyolefins includes providing two or more reactor trainsconfigured in parallel wherein the two or more reactor trains producetwo or more high molecular weight polyolefin (base polymer) blendcomponents and all plasticizer components are made off-line but blendedin-line. For the two or more parallel reactor trains producing the twoor more high molecular weight polyolefin(s), the process includescontacting olefin monomer(s) with catalyst systems, optionalcomonomer(s), optional scavenger(s), and optional diluent(s) orsolvent(s); the polymerization performed in at least one of the two ormore reactor trains, and advantageously in all reactor trains, at atemperature above the solid-fluid phase transition temperature of thepolymerization system and at a pressure no lower than the solid-fluidphase transition pressure and no lower than 10 MPa below the cloud pointpressure of the polymerization system and less than 1500 MPa,particularly between 10 and 300 MPa, still more particularly between 20and 250 MPa; wherein the polymerization system comprises the monomer,any comonomer(s), any scavenger(s), any diluent(s) or solvent(s)present, and the polyolefin-based polymer product and where the catalystsystem comprises catalyst precursor compound(s), activator(s), andoptional support(s); and forming a polyolefin/polymer reactor effluentstream including a polyolefin blend component (base polymer blendcomponent) dissolved in the effluent dense fluid polymerization system.The one or more off-line-produced plasticizers are pumped in theirliquid, molten, or dissolved state into one or more polymer-containingeffluent streams to produce an in-line-plasticized polymer blend. Theblending point for combining the polymer- and plasticizer-containingstreams may be anywhere downstream of the reactor bank of the disclosedin-line polymer blending processes. Advantageously, the one or moreplasticizers are blended with a base polymer containing stream thatstill contains at least some of the low molecular weight components,such as the monomers and the optional inert solvents/diluents of thepolymerization system, to facilitate the blending process by the virtueof reduced viscosity. The said advantageous mixing points of thedisclosed in-line blending processes exist downstream of the reactorsand upstream of the extruder or devolatizing extruder of the productfinishing section of the processes disclosed herein, particularly,downstream of the reactors and upstream of or in the low-pressureseparator deployed just before the said extruder or devolatizingextruder of the finishing section. Thus, this embodiment of thedisclosed processes blend the plasticizers and the base polymer in-line,i.e., before the base polymer is recovered in its essentially pure,solid form but do not produce any of the employed plasticizers in-line.In some embodiments, the two or more polyolefin effluent streams fromthe two or more parallel reactor trains and the one or moreoff-line-produced plasticizer feed streams are combined downstream ofthe reactor bank and upstream of or in a phase separator thatsimultaneously provides blending of the in-line blend components andseparation of the monomer(s) and inert diluents(s) or solvents(s) fromthe base polyolefin blend component(s) and plasticizer blendcomponent(s) by bringing the combined reactor effluent and plasticizerfeed streams below the cloud point of the mixture while maintaining saidmixed streams above the solid-fluid phase transition point by adjustingthe temperature and pressure of the effluent streams individually (i.e.,before the mixing point), or combined (i.e., after the mixing point);when the reactor effluents are combined upstream of a phase separator,optionally passing the mixed reactor effluent streams through one ormore static mixers before entering the said separator to enhance mixing;maintaining the pressure within the separator vessel below the cloudpoint pressure to form two fluid phases comprising apolyolefin-plasticizer-rich fluid phase and a monomer-rich fluid phase;maintaining the temperature in the separator above the solid-fluid phasetransition temperature to allow the settling to the bottom and theformation of a continuous layer at the bottom of a denser well-mixedfluid polyolefin-plasticizer-rich blend phase and allowing the rising tothe top and the formation of a continuous layer of a lower-densitymonomer-solvent-rich phase at the top; separating a monomer-rich phasefrom a polyolefin-plasticizer-rich blend phase and recycling theseparated monomer-rich phase directly or after further treatment to thepolymerization trains; optionally, further reducing the pressure of thesaid first polyolefin-plasticizer-rich blend phase upstream of or in alow-pressure separator to achieve another fluid-fluid separation into amore concentrated polyolefin-plasticizer-rich fluid phase and anothermonomer-rich phase while maintaining the temperature above thesolid-fluid phase transition temperature by optionally further heatingthe first polyolefin-plasticizer-rich blend stream; optionally, addingcatalyst killer(s), and/or polymer modifier(s) and/or additive(s) intheir dense fluid state (i.e., liquid, supercritical fluid, molten, ordissolved state) to the base polyolefin- and/or plasticizer-containingeffluent stream(s) at any desired point downstream of the first pressureletdown valves in any of the individual or combined effluent streams ofthe reactor trains to in the reactor bank of the disclosed processes.The polyolefin-plasticizer-rich phase from the separator section of thein-line blending process is then conveyed to a downstream finishingstage for further monomer stripping, drying and/or pelletizing to formthe plasticized polyolefin blend product of the in-line blendingprocess.

Note that the in-line blending processes disclosed herein comprise apolymerization section or polymerization reactor bank or reactor bankand at least one monomer-polymer separator vessel, called theseparator-blending vessel, or separator-blender, or high-pressureseparator or high-pressure separator-blender. In some embodiments, oneor more reactor trains produce plasticizers. In those embodiments, theplasticizer-producing reactor trains also belong to the polymerizationsection, i.e., those reactors are also part of the polymerizationreactor bank or reactor bank even if they are referred to as plasticizertrains in order to differentiate them from the reactor trains producingthe high molecular weight base polymer blending components (the lattertrains are sometimes referred to as polymer trains). Theseparator-blender serves as both a separator and a blender for thereactor effluents of the two or more parallel reactor trains in thereactor bank in which at least one of the reactor trains employs ahomogeneous fluid polymerization system (i.e., defined as a homogeneoussupercritical or a solution polymerization process). It is alsobeneficial to the proper operation of the in-line blending processesdisclosed herein to bring the polymerization system in each reactortrain effluent into a homogeneous state upstream of theseparator-blending vessel. Thus, when one or more in-line blendingcomponents is/are produced in a particle-forming polymerization process,such as, for example bulk propylene slurry polymerization withZiegler-Natta or supported metallocene catalysts, the so-produced solidpolymer pellets need to be homogeneously dissolved in the reactoreffluent before entering the separator-blending vessel. This can beaccomplished by, for example, pumping the reactor effluent slurry into ahigher-temperature/higher-pressure dissolution zone that brings thereactor effluent above the solid-fluid phase transition temperaturecreating a stream in which the reaction product is homogeneouslydissolved. Although any and all combinations of reactor operation modesmay be included in the in-line blending processes disclosed herein, itis advantageous that at least one reactor train operates in ahomogeneous fluid phase and more advantageous if all reactor operationsoperate in the homogenous fluid phase for economic and processsimplicity reasons. Bulk homogeneous fluid phase polymerizations such asbulk homogeneous supercritical or bulk solution polymerizations areparticularly advantageous.

The methods of fluid phase in-line-plasticized polymer blendingdisclosed herein offer significant advantages relative to prior artmethods of blending polymers and plasticizers. One or more of theadvantages of the disclosed method of in-line plasticized polymerblending include, but are not limited to, improved polymer-plasticizerblend homogeneity because of molecular-level mixing of blend components,improved cost of manufacture because of savings from avoidance of thereprocessing cost associated with conventional off-line blendingprocesses that start with the separately produced solid, pelletizedpolymer and plasticizer blend components, and because of the ease andsimplicity of blending polymers at substantially reduced viscosities dueto the presence of substantial amounts of monomers and optionallysolvents in the blending step; flexibility of adjusting blend ratios andtherefore blend properties in-line; flexibility in adjusting productionrates of the blend components; flexibility in independently controllingfor each reactor the residence time, monomer composition and conversion,catalyst choice, catalyst concentration, temperature and pressure;improved blend quality; flexibility in making a broader slate ofplasticized polymer products in the same plant; reduced process cost byutilizing the monomer-polymer separator(s) for product blending and, insome embodiments, for product buffering to allow better control of blendratio.

In-Line Blending Process Overview:

Polyolefins are used in a large number of different applications. Eachof these applications requires a different balance between thestiffness, elasticity, and toughness of the polymer. Ideally, polymerswould be custom-tailored to the different needs of each customer. One ofthe methods enabling product tailoring involves the blending ofindividual polymer components. The ability to adjust thestiffness-elasticity-toughness balance of polyolefins provides for theability to meet the needs of a broad range of applications and thus toexpand the potential of polyolefins in delivering desired performance atreduced cost. The stiffness-elasticity-toughness balance may be alteredby changing the molecular structure of polymers by changing theircomposition (i.e. making copolymers), stereoregularity, molecularweight, etc. The stiffness elasticity-toughness may also be readilyshifted by making blends of polymers, blends of polymers andplasticizers or by producing composites. The in-line blending processesdisclosed herein relate to making polymer-plasticizer blends, alsoreferred to as plasticized polymers. The one or more base polymercomponents for blending with one or more plasticizers are generally highmolecular weight polyolefin resins, such as polypropylenes (particularlyisotactic and syndiotactic polypropylenes), polyethylene,ethylene-propylene copolymers, copolymers of propylene and C₄ to C₂₀olefins (particularly C₅ to C₂₀ linear alpha-olefins), copolymers ofethylene and C₄ to C₂₀ olefins (particularly C₅ to C₂₀ linearalpha-olefins), polymers with long-chain branching (LCB), and cyclicolefin copolymers (COC's) made of ethylene and a cyclic olefin, such asnorbornene, cyclopentene, cyclohexene, and the like. When the basepolymer comprises soft copolymer components, they are always used incombination with high molecular weight high crystallinity base polymercomponents, such as polypropylene or polyethylene. The one or moreplasticizer components that are either produced in-line and/or off-linebut always blended in-line include polyolefin oligomers, mineral oils,lubricant basestocks, and soft polyolefins. The one or moreexternally-produced plasticizers may be optionally used in connectionwith the one or more in-line-produced plasticizers. Alternatively, theone or more externally-produced plasticizers may be used for in-lineblending to produce in-line-plasticized polymers without employingin-line-produced plasticizers.

Plasticizers conducive to off-line production and in-line blendinginclude all types of useful plasticizers listed above. Plasticizersconducive to in-line production and in-line blending, on the other hand,typically represent a shorter list. Thus, for example, plasticizersproduced by separation from natural resources, such as, paraffin oilsand waxes, Group I, II, and III lube base stocks, etc. made from crudeoil, would obviously not be produced in-line. Some syntheticplasticizers, made primarily for other markets, like phthalates,mellitates, adipates, etc. made for PVC applications, would be alsoproduced off-line. There are also instances, when the in-line productionof plasticizers is impractical for compatibility reasons due topotential cross-contamination. For example, in-line processes to makeplasticizers involving superacids, and oxygen-containing compounds aretypically not practical when the one or more base polymers are producedby using highly poison-sensitive single-site catalysts, such asmetallocenes, Ziegler-Natta catalysts, etc., due to the high potentialfor catalyst poisoning and consequentially, due to the need forexpensive purification methods in the feed recycle lines. Otherpractical reasons, for example retrofitting existing plants, orunfavorable economics in certain locations due to feedstock coststructure, etc., may also favor in-line blending of off-line-producedplasticizers even if they could be economically produced in-line atother locations. For the above reasons, the disclosed processes forin-line blending of plasticizers with base polymers to producein-line-plasticized polymers offer three options: (1) in-line productionof all employed plasticizer blending components; (2) in-line productionof one or more plasticizer blending components employed in combinationwith one or more off-line-produced plasticizer blending components; (3)all plasticizer blending components employed produced off-line. Itshould be also noted that the in-line blending processes disclosedherein are deployed in combination with two or more parallelpolymerization reactor trains. Consequently, by our definitions ofparallel polymerization reactor trains (vide supra), the number of basepolymer components may be one or more for options (1) and (2) and may betwo or more for option (3). Furthermore, when all in-line-blendedplasticizers are produced off-line (option (3)), the base polymercomprise two or more high molecular weight in-line polymer blendingcomponents. The processes described by options (1) and (2), on the otherhand, may comprise one or more high molecular weight in-line polymerblending components. When two or more high molecular weight in-linepolymer blending components are produced, these blending components mayessentially be the same or may be different. The utility of makingessentially the same high molecular weight in-line polymer blendingcomponents in more than one reactor trains could be increased capacity.

One of the important functions of plasticizers is their ability toreduce the glass transition temperature of polymer-plasticizer blends.They perform this function by themselves having significantly lowerglass transition temperatures as compared to that of the base polymer.Another important function of plasticizers is to reduce blend viscosityduring processing. Again, they perform this function by themselveshaving significantly lower viscosity as compared to that of the basepolymers. Both of these properties strongly influenced by molecularweight. Namely, lower molecular weight lowers both and thus isadvantageous. For that reason, plasticizers are advantageously lowmolecular weight (<30 kg/mol Mw) oligomers (i.e., have less than 76monomer units) that are liquid at ambient conditions although forincreased permanence/lower volatility, polymers are also used asplasticizers commercially.

Disclosed herein are advantageous processes for direct in-line polymerblend production in an integrated parallel multi-reactor polymerizationwherein the in-line blending step of combining one or more polyolefinbase polymers with one or more plasticizers is achieved downstream ofthe reactors and upstream of the extruder or devolatalizing extruder ofthe finishing section of the process and wherein at least one,advantageously all, reactor trains operate with a homogeneouspolymerization system. The production of plasticized polymer blends inthe polymerization plant is facilitated when the polymer and plasticizerblend components, particularly when the highly viscous polymer blendcomponents, are dissolved in the polymerization system since thesmall-molecule components, such as monomers and optionalsolvents/diluents of the polymerization system reduce viscosity thusallowing molecular level blending in a lower-shear/lower-energy process.The presence of low molecular weight diluents also lowers thesolid-fluid phase transition temperature allowing lower-temperatureblending operations. Hence, using the reactor effluents wherein thepolymer and plasticizer blending components are present in a dissolveddense fluid state may be advantageous to downstream blending operations.Thus, the polymerization reactors for the high molecular weight polymerand/or plasticizer advantageously may be of the homogeneoussupercritical process, the solution process type, or a combinationthereof in order to provide the base polymer and the plasticizer forblending in a dense fluid state in the direct reactor effluents suitablefor the in-line blending process. Bulk homogeneous supercritical andbulk solution polymerization processes are particularly useful forproducing base polymer and plasticizer blend components due to thesimplicity of the monomer recycle loop and due to the enhancements inreactor productivity and base polymer properties, such as molecularweight and melting behavior, as will become apparent from the followingdiscussions. The processes disclosed herein can also utilize certainother polymerization reactors making base polymer blend components, forexample, in the form of a slurry, wherein the polymers form solidpellets in a dense fluid polymerization system (for an exemplary processconfiguration comprising a slurry polymerization reactor train see FIG.10). In such instances, a dissolution stage is added between thepolymerization reactor train and the separator-blending vessel. Thisdissolution stage typically consists of a pump followed by a heater tobring the reactor effluent above the solid-fluid phase transitionconditions affording a stream that contains the polymer blendingcomponent homogeneously dissolved in the dense fluid polymerizationsystem. In order to facilitate the dissolution of the polymer pellets,increased shearing may be applied, which typically is provided bystirring or by pumping. Because of the added processing and investmentcosts of such reactor operations, homogeneous polymerization processes,such as homogeneous supercritical or solution polymerization, aretypically cost-advantaged and thus advantageous to produce the in-linepolymer blending components. At least some fraction of the low molecularweight components, such as unused monomers and the optional inertsolvents/diluents are separated for recycle from the product polymersand plasticizers in one or more phase separators. Other separationmethods, such as distillation, vacuum drying, etc. may also be deployed,particularly in the plasticizer production trains and in the productfinishing section of the disclosed processes. At least one of the one ormore phase separators also serves as a blending vessel to form apolymer-plasticizer-rich phase to ultimately yield thein-line-plasticized polyolefin final product. Advantageousconfigurations and operation modes for the feed-product phase separationsection are disclosed in U.S. Patent Application No. 60/876,193 filed onDec. 20, 2006, herein incorporated by reference in its entirety.

One or more plasticizers for in-line blending may be produced in-lineusing the homogeneous fluid-phase synthesis processes disclosed herein.In particular, homogeneous dense supercritical phase or solution phaseprocessing may be utilized to synthesize selected plasticizers disclosedherein in one or more of the parallel reactor trains of the disclosedin-line polymerization and blending processes. Advantageously, allparallel trains, i.e., both the base polymer and plasticizer trains, runwith single-site catalysts as described in the section titled “CatalystSystem Overview” (vide infra) but other catalyst types may also be usedif so desired. When the catalyst systems of the plasticizer and basepolymer reactor trains have incompatible components and/or the monomerpools of the plasticizer and base polymer reactor trains have no commonmonomer members, it may be advantageous to recover the one or moreplasticizers in essentially pure form before blending them with the basepolymer containing streams. The full recovery of the one or moreplasticizer components is particularly advantageous when one of more ofthe above-stated conditions are met and the fully recovered plasticizerblending component is a liquid. Note, however, that in order tofacilitate the in-line blending, it is always performed in a fluid phasediluted by low molecular weight components, such as unreacted monomersand optional one or more inert solvents/diluents. Therefore, it isadvantageous to blend the plasticizer-containing streams before the saidlow molecular weight components of the polymerization system of the basepolymer containing effluents are fully removed. The disclosed processesoften blend the effluents of the base polymer producing reactor trainsbefore any of the low-molecular weight components, such as the unreactedmonomers and the optional inert solvents/diluents, are removed from thesaid base polymer containing straight reactor effluents. As statedbefore, at least some fraction of the low molecular weight components,such as unused monomers and the optional inert solvents/diluents, areseparated for recycle from the product polymers and plasticizers in oneor more phase separators. Other separation methods, such asdistillation, vacuum drying, etc. may also be deployed, particularly inthe plasticizer production trains and in the product finishing sectionof the disclosed processes. At least one of the one or more phaseseparators also serves as a blending vessel to form apolymer-plasticizer-rich phase to ultimately yield thein-line-plasticized polyolefin final product. Advantageousconfigurations and operation modes for the feed-product phase separationsection are disclosed in U.S. Patent Application No. 60/876,193 filed onDec. 20, 2006, herein incorporated by reference in its entirety.

Optionally, other plasticizers that are not conducive to in-linereacting, but are conductive to in-line blending may be further added tothe polymer-plasticizer blend. These other plasticizers may be stored inone or more polymer additive storage tanks. Non-limiting exemplaryplasticizers that are not conducive to in-line production, but areconducive to in-line blending include paraffin oils and waxes(n-paraffins, isoparaffins, paraffin blends), mineral oils, processoils, high purity hydrocarbon fluids, lubricant basestocks, and othersynthetic or natural oils. Off-line-produced liquid plasticizers can bedirectly pumped to the mixing point of the in-line blending process.Solid plasticizers are typically dissolved before delivering them to themixing point advantageously using a solvent and/or monomer that is alsoused in the polymerization bank. Before bringing them to the mixingpoint, the plasticizer feeds are typically heated to the temperature ofthe polymerization product stream to be blended with the plasticizerfeed.

As described herein before, the disclosed in-line blending process forplasticized polymers comprises a polymerization process that providesone or more of the high molecular weight base polymers and in someembodiments one or more of the plasticizers in a homogeneous fluid stateused for in-line blending. Therefore, if the polymerization reaction iscarried out at conditions that form solid polymer particles, such as,for example, slurry polymerization, an additional step is required tobring the solid in-line polymer blending component into a dissolvedfluid state before feeding the polymer-containing stream to theseparator-blender section of the disclosed polymer-plasticizer blendingprocess (for an exemplary process configuration comprising a slurrypolymerization reactor train see FIG. 10). This can be accomplished by,for example, heating the reactor effluent comprising the solid polymericproduct, unused monomer(s), and optional inert diluent(s)/solvent(s)above the solid-liquid phase transition temperature. However, forsimpler and thus lower cost operations, the polymerization reaction istypically carried out at conditions where the product polymer(s) is/aredissolved in the dense fluid polymerization system comprising one ormore monomers, the polymeric product(s), and—optionally—one or moreinert solvents, and—optionally—one or more scavengers. Fluid-phaseoperations have some further advantages from certain product quality andoperation stability perspectives since they do not require supportedcatalysts that significantly increase the ash level of the products andcan cause fouling and excessive wear of downstream process hardware. Thefluid reaction medium may form one single fluid phase or two fluidphases in the reactor. For more robust and simpler reactor operations,conditions affording a single fluid phase in the reactor, i.e. operatingabove the cloud point conditions, are advantageous.

In one embodiment of the plasticized polymer blending processesdisclosed herein, the blending of the one or more polymer reactoreffluent streams with the one or more plasticizer effluent streamsoccurs simultaneously with product separation in a single downstreamseparator-blending vessel. The separator-blender operates at conditionsthat lead to the formation of two fluid phases: the upper oneessentially consisting of the low-molecular weight components of thepolymerization systems, predominantly the monomer(s) and the optionalsolvent(s) of the polymer and plasticizer reaction processes, while thelower one is a plasticized polymer-rich phase. In order to create theconditions that lead to the formation of two fluid phases in theseparator-blender, the temperatures of the reactor effluents are oftenfirst increased to provide the heat for staying above the solid-fluidphase transition temperature of the to-be-formed plasticizedpolymer-rich fluid phase. After adjusting the heat contents of thereactor effluents, their pressures are typically reduced to bring thetemperature and pressure of the combined effluent stream to a conditionthat corresponds to two fluid (liquid-liquid or supercriticalfluid-supercritical fluid) phases in the phase diagram. The blendingprocess may be aided by optional static mixer(s) downstream of themixing point of the polymer-containing and plasticizer-containingeffluents but upstream of the separator-blending vessel. The homogeneousfluid blending of the individual polymer and plasticizer components andthe separation of the monomer- and plasticized-polymer-rich phases areaccomplished in the same vessel eliminating the need for a separateblending vessel and blending process step. The bulk of the monomer(s)and the optional solvent(s) separated from the polymer and plasticizeris then recycled back into the polymer and plasticizer polymerizationreactor bank of the plant.

In another embodiment of the in-line blending processes disclosedherein, one or more reactor effluent streams containing the dissolvedpolymer or plasticizer blend components are fed to independentseparators or separation vessels (also referred to as single-streamhigh-pressure separators) upstream of the separator-blending vessel forseparation of a polymer-enriched or plasticizer-enriched stream fromsome fraction of the monomer and the optional solvent/diluent content ofthe said streams. Such single-stream high-pressure separators deployedupstream of the separator-blending vessel (high-pressure separator) inessence afford a partial recovery of the monomer and the optionalsolvent present in the reactor effluent thus allowing their recovery andrecycle before being mixed with monomers and optional solvents used inother reactor trains. Such processes may be advantageous by eliminatingthe need for separating mixed monomer and optional solvent streamsbefore recycling them to the appropriate reactor trains for polymer andplasticizer of the reactor bank as disclosed in U.S. Pat. Appl. No.60/905,247 filed on Mar. 6, 2007 incorporated herein in its entirety byreference. The polymer-enriched streams and plasticizer-enriched streamsfrom each of these single-stream separators are blended in one separatorvessel that serves both as a separator for one of the reactor trains andas a blender for the entire reactor bank (separator-blending vessel). Inthis embodiment, the operation conditions of one or more single-streamseparators upstream of the separator-blending vessel may be adjusted toyield one or more polymer-enriched streams and/or one or moreplasticizer-enriched streams that still contain enough low molecularweight components, such as monomers and optional inert solvents to keepthe viscosity of these streams much below that of the essentially puremolten polymers or plasticizers thus facilitating the mixing of thepolymer and plasticizer components in the separator-blender. The one ormore separators feeding the separator-blending vessel may also serve asbuffer vessels affording an improved control of the blend ratio bycompensating for the small but inevitable fluctuations in the productionof the individual in-line polymer and plasticizer blend components. Thebuffer capacity of these vessels is defined by the volume between themaximum and minimum levels of the separated polymer-enriched orplasticizer-enriched lower phase.

The blending processes disclosed herein provide for the individualcomponents of the plasticized polymer blend to be made in a bank ofparallel reactors. One or more of the parallel reactor trains produceone or more polymer blend components and one or more of the parallelreactor trains produce one or more plasticizer blend components forsubsequent downstream in-line blending. Such direct blend production maybe advantageously achieved in polymerization processes that operate in ahomogeneous dense fluid phase, i.e. above the fluid-solid phasetransition limits. The in-line blending process disclosed has at leastone reactor train making a high molecular weight base polymer blendcomponent that operates in a homogeneous dense fluid phase.Advantageously, all reactor trains in the reactor bank of the disclosedprocesses operate in a homogeneous dense fluid phase. Polymerizationprocesses that operate in a homogenous dense fluid phase use eitherinert solvent(s) or monomer(s) or their mixtures as a solvent/diluent intheir liquid or supercritical state. Hence, such parallel reactorsoperate with polymerization systems in their homogeneous supercriticalor in their liquid state. In both the supercritical and liquid operationmodes, the process may be a bulk polymerization process operating withless than 40 wt %, or less than 30 wt %, or less than 20 wt % or lessthan 10 wt % or less than 5 wt % of inert solvent present in thereactor, and in some embodiments, essentially free (less than 1 wt %) ofinert solvents. In one embodiment of the disclosed process, the one ormore polymer reactors and one more plasticizer reactors operate at bulkhomogeneous supercritical conditions as has been disclosed in U.S.patent application Ser. Nos. 11/433,889 and 11/177,004, hereinincorporated by reference in their entirety.

In another embodiment, one or more polymer reactor trains and one ormore plasticizer reactor trains operate at conditions where the polymerand plasticizer dissolution is substantially aided by an inert solvent(solution process where the polymerization medium contains more than 40wt % solvent, typically more than 60 wt % solvent) as has been disclosedin PCT Publication No. WO 2006/044149, herein incorporated by referencein its entirety. In yet another embodiment, one or more of the polymeror plasticizer reactors included in the parallel bank of reactorsoperate in the homogeneous supercritical state and one or more of thepolymer or plasticizer reactors included in the parallel bank ofreactors operate in the solution state (combination of solution processand homogeneous supercritical process reactors). Both homogenoussolution and homogeneous supercritical polymerization processes providepolymers dissolved in a fluid state, which is required for thedownstream in-line blending of plasticized polymers. Both homogenoussolution and homogeneous supercritical processes providing polymers andplasticizers in a homogeneous fluid state may be performed in a bulkmonomer phase using essentially pure monomer(s) as solvent or may keepthe polymer or plasticizer in the homogeneous fluid state by employingan inert solvent in substantial concentrations (i.e., 60 wt % or more).The homogenous solution process provides for a polymer- orplasticizer-containing liquid phase either in an inert solvent or in theessentially neat monomer or in their mixture in their liquid state. Thehomogeneous supercritical process provides for the fluid state bydissolving the polymeric base polymer or plasticizer product either inan inert solvent or in the essentially neat monomer or in their mixturein their supercritical state.

In another embodiment, one or more polymer or plasticizer reactorsincluded in the parallel realtor bank operate in homogeneoussupercritical or solution mode and one or more polymer reactor trainsoperate in the slurry mode (combination of slurry and homogeneoussupercritical or combination of slurry and solution processes). Thedense fluid phase(s) of the slurry polymerization process(es) deployedin one or more polymer trains of the disclosed in-line blending processcan be either in its/their liquid or in its/their supercritical state.Before bringing the effluent(s) of the slurry train(s) to theseparator-blending vessel (high-pressure separator) of the in-lineblending process, the effluents are treated to fully dissolve theslurried polymer blend component. Aside this dissolution step, the otheraspects of the in-line blending process disclosed herein are notaffected by having a particle-forming polymerization reactors in thereactor bank. This embodiment may provide product advantages in certainapplications due to the ability of the slurry process to produce certainhighly crystalline homopolymer blend components, such as isotacticpolypropylene made with Ziegler-Natta catalysts. It is, however,typically more expensive due to the added processing and investmentcost. The optimal choice between the different reactor configurations ofthe disclosed process depends on the target product slate or even onsome production site-specific issues, like, for example, the utilizationof existing polymerization facilities. The optimal configuration can bedetermined by standard techniques well known in the art of chemicalengineering.

The parallel reactor configuration disclosed herein permits forflexibility in independently controlling for each polymer andplasticizer reactor, the residence time, monomer composition andconversion, catalyst choice, solvent/diluent composition andconcentration, and catalyst concentration. It also makes the independentcontrol of reaction temperature and pressure easier thus enhancing thecontrol of the synthesis processes yielding the individual in-linepolymer and plasticizer blend components.

U.S. patent application Ser. Nos. 11/433,889 and 11/177,004 disclose aflexible polymerization platform for the supercritical propylenepolymerization process (also referred to herein as the “supercriticalprocess”). In the referred supercritical propylene polymerizationprocess, polymerization is carried out in a substantially supercriticalmonomer medium, thus it is a bulk supercritical polymerization process.The polymer is in a dissolved state in the reactor and in the reactoreffluent thus making the reactor effluent suitable for a directdownstream blending operation prior to recovering the polymeric productsin their solid pelletized or baled form. U.S. patent application Ser.Nos. 11/433,889 and 11/177,004 also teach that the supercriticalpolymerization process provides an advantageous means to the so-calledsolution processes in its ability to produce highly crystalline, highmolecular weight (i.e. low melt-flow rate) isotactic propylenehomopolymers. Unlike gas phase and slurry polymerization processes, thesupercritical process may also produce ethylene-propylene copolymers andpropylene homopolymers with reduced tacticity, and thus reduced polymermelting point without fouling. As previously referenced, U.S. patentapplication Ser. Nos. 11/433,889 and 11/177,004 are incorporated byreference in their entirety herein.

Advantageous plasticized polymer blends are often composed of a blend of(a) high molecular weight highly crystalline polymer component(s) and(a) low molecular weight low crystallinity oligomer/polymercomponent(s). Slurry and gas phase polymerization processes may providefor high molecular weight, highly crystalline polymers, but not for lowcrystallinity products because the polymer pellets stick togethercausing fouling of the reactor. In contrast, solution polymerizationprocesses may provide for low crystallinity products because the polymeris present in solution in the reactor, and therefore cannot foul it.However, the solution process has limitations in producing highlycrystalline, high molecular weight products with higher melting point.One limitation of the solution process is that it typically cannotproduce high MW products that also have high melting point, and if itcould, such products tend to crystallize in the reactor and causefouling. In contrast, the homogeneous supercritical process may providefor both high crystallinity/high melting point and low crystallinity/lowmelting point polymers without fouling. These products can also be madewith any desired, low or high, molecular weight. It also generates thepolymer blend components in a dissolved state in the polymerizationsystem allowing direct blending without the need for a dissolution step.These attributes make it a particularly advantageous polymerizationprocess for the in-line blending processes disclosed herein.Notwithstanding, any combination of polymerization processes operatingwith dense polymerization systems may be deployed in the in-lineblending processes disclosed herein as long as at least one of thepolymer and plasticizer reactor trains operates with a homogeneouspolymerization system. Homogeneous operation is ensured by operatingabove the solid-fluid phase transition point, advantageously not lowerthan 10 MPa below the cloud point of the polymerization system.

The monomers for use in the bank of parallel reactors disclosed hereinmay be any olefinic compounds containing at least one aliphatic doublebond. The olefin group may be unsubstituted or substituted by one ormore aliphatic or aromatic group(s) and may be part of an open chain ora non-aromatic ring. Exemplary, but not limiting, olefins include alphaand internal linear or branched olefins and their blends, such asethylene, propylene, butenes, pentenes, hexenes, heptenes, octenes,nonenes, decenes, dodecenes, styrenes, non-conjugated dienes,cyclohexene, norbornene, and the like. Exemplary, but not limiting,non-polymerizing (inert) fluid components serving as diluents/solventsinclude light paraffinic and aromatic hydrocarbons and their blends,such as butanes, pentanes, hexanes, heptanes, octanes, toluene, xylenes,cyclopentane, cyclohexane, fluorocarbons, hydrofluorocarbons, etc.

The conditions in the polymerization reactors of the aforementionedolefin polymerization process may be established such that the entirereactor content, including the monomer(s), optional non-polymerizingfluid, catalyst system(s), optional scavenger(s) and polymeric products,is in a homogeneous fluid, and advantageously in a single homogeneousfluid state. In certain embodiments, the conditions in the reactors ofthe aforementioned process may be set such that the reactor contents arein their supercritical fluid state, and advantageously in a singlehomogeneous supercritical fluid state.

The upper limit for temperature is determined by the product propertiesthat are strongly influenced by the reaction temperature (for anexample, see FIG. 2). Since polymers with higher molecular weightsand/or higher melting points are desired for the base polymer blendcomponents, high polymerization temperatures (>250° C.) are generallynot advantageous. Increased temperatures can also degrade most knowncatalytic systems, providing another reason for avoiding excessivepolymerization temperatures. However, high polymerization temperatures(>250° C.) may be advantageous for producing plasticizer componentsbecause of the desirability for low molecular weight. FIG. 5 provides anexample of how catalytic activity is impacted by increasingpolymerization temperature. At the current state of the art ofpolymerization, polymerization temperatures above 350° C. are notrecommended. For the slurry polymerization processes, the uppertemperature limits of polymerization are also influenced by thesolid-fluid phase transition conditions since running near thesolid-fluid phase transition line leads to fouling. For that reason,slurry operations not higher than 5° C. below the solid-fluid phasetransition are advantageous, not higher than 10° C. below thesolid-fluid phase transition are particularly advantageous.

The lower limits of reaction temperature are determined by the desiredpolymer and/or plasticizer properties. Lower temperatures generallyfavor higher crystallinity and higher molecular weight (for an example,see FIG. 2). For homogeneous polymerization processes, the lower limitsof reaction temperature are also determined by the solid-fluid phasetransition temperature. Running the reactors below the solid-fluid phasetransition temperature of the reaction mixture may lead to operationproblems due to fouling. For the production of highly crystallinepolypropylenes (melting peak temperatures >150° C.) in bulk homogeneoussupercritical propylene polymerization processes, the minimum operatingtemperature is about 95-100° C. In the production of lower meltingcopolymers, such as ethylene-propylene and ethylene-hexene-1 copolymers,significantly lower reactor temperatures, e.g., 90° C. or even lower,may be readily used without fouling. The application of certain inertsolvents may further reduce the minimum operation temperature of thefouling-free operation regime, although, as discussed earlier, thesubstantial presence of inert solvents also tends to limit the productmolecular weight and often the melting peak temperature. It alsoincreases production cost due to the need for solvent handling.

The critical temperature and pressure of the polymerization systems aredifferent from the critical values of pure components, and thussupercritical operations at temperatures lower than the criticaltemperature of pure propylene and C₄ plus monomers (e.g., 92° C. forpropylene) are possible and disclosed herein. Additionally,near-amorphous and amorphous materials with low melting points may beproduced without fouling even below the critical temperature of thereactor blends, i.e., at temperatures that correspond to the condensedliquid state of the polymerization system in the reactor. In theseinstances, the operation temperature may be below the bubble point ofthe reaction mixture and thus the reactor operates at what is oftenreferred to as liquid-filled conditions. In some instances, suchoperation mode could be desired to achieve high molecular weight (MW)and thus low melt flow rate (MFR), particularly in the manufacture ofhigh molecular weight copolymers, such as propylene-ethylene orethylene-higher olefin or propylene-higher olefin copolymers. Thus,reactor operations under conditions at which the polymeric products aredissolved in the monomer or monomer blend present in its liquid state,also known as bulk solution polymerization, are also disclosed herein.

Reaction Temperature for Homogeneous Fluid Phase Polymerizations:

The reaction process temperature should be above the solid-fluid phasetransition temperature of the polymer-containing and (when theplasticizer is a solid at ambient temperature) theplasticizer-containing fluid reaction systems at the reactor pressure,or at least 2° C. above the solid-fluid phase transition temperature ofthe polymer-containing and plasticizer-containing fluid reaction systemat the reactor pressure, or at least 5° C. above the solid-fluid phasetransition temperature of the polymer-containing andplasticizer-containing fluid reaction system at the reactor pressure, orat least 10° C. above the solid-fluid phase transformation point of thepolymer-containing and plasticizer-containing fluid reaction system atthe reactor pressure. In another embodiment, the reaction processtemperature should be above the cloud point of the single-phase fluidreaction system at the reactor pressure, or 2° C. or more above thecloud point of the fluid reaction system at the reactor pressure. Instill another embodiment, the reaction process temperature should bebetween 40 and 350° C., or between 50 and 250° C., or between 60 and250° C., or between 70 and 250° C., or between 80 and 250° C., orbetween 90 and 220° C., or between 93 and 220° C. Exemplary lowerreaction temperature limits are 40, or 50, or 60, or 70, or 80, or 90,or 95, or 100, or 110, or 120° C. Exemplary upper reaction temperaturelimits are 350, or 250, or 240, or 230, or 220, or 210, or 200° C.

In certain embodiments, polymerization is performed in a supercriticalpolymerization system. In such embodiments, the reaction temperature isabove the critical temperature of the polymerization system. In someembodiments, some or all reactors operate at homogeneous supercriticalpolymerization conditions Said homogeneous supercritical polymerizationsof the in-line blending processes disclosed herein may be carried out atthe following temperatures: In one embodiment, the temperature is abovethe solid-fluid phase transition temperature of the polymer-containingand plasticizer-containing fluid reaction medium at the reactor pressureor at least 5° C. above the solid-fluid phase transition temperature ofthe polymer-containing and plasticizer-containing fluid reaction mediumat the reactor pressure, or at least 10° C. above the solid-fluid phasetransformation point of the polymer-containing andplasticizer-containing fluid reaction medium at the reactor pressure. Inanother embodiment, the temperature is above the cloud point of thesingle-phase fluid reaction medium at the reactor pressure, or 2° C. ormore above the cloud point of the fluid reaction medium at the reactorpressure.

Reaction Pressure for Homogeneous Fluid Phase Polymerizations:

The maximum reactor pressure may be determined by process economics,since both the investment and operating expenses increase withincreasing pressure. The minimum pressure limit for the production ofthe individual polymer and plasticizer blend components disclosed hereinis set by the desired product properties, such as molecular weight (MW)and melt flow rate (MFR) (see, for example, FIG. 3).

Reducing process pressures in homogeneous polymerizations may lead tophase separation creating a polymer-rich or plasticizer-rich and apolymer-lean or plasticizer-lean fluid phase. In well-stirred reactors,where mass transport is sufficiently high due to efficient mixing of thetwo phases, product qualities may not be impacted by such fluid-fluidphase separation. Therefore, polymerization process conditions underwhich there is a polymer-rich or plasticizer-rich and a polymer-lean orplasticizer-lean phase are provided herein as long as both phases areabove the solid-fluid phase separation limit thus preventing fouling andare well mixed thus preventing substantial mass transfer limitationleading to poorly controlled increases in molecular weight and/orcompositional distributions. Generally, however, operating in asingle-phase dense fluid polymerization is advantageous because it isless prone to fouling and provides better heat transfer properties.

Exemplary, but not limiting, process pressures, are between 1 MPa (0.15kpsi) to 1500 MPa (217 kpsi), and more particularly between 1 and 500MPa (0.15 and 72.5 kpsi). In one embodiment, the polymerization processpressure should be no lower than the solid-fluid phase transitionpressure of the polymer-containing or plasticizer-containing fluidpolymerization system at the reactor temperature. In another embodiment,the polymerization process pressure should be no lower than 10, or 5, or1, or 0.1, or 0.01 MPa below the cloud point of the fluid polymerizationsystem at the reactor temperature and less than 1500 MPa. In stillanother embodiment, the polymerization process pressure should bebetween 10 and 500 MPa, or between 10 and 300 MPa, or between 20 and 250MPa. Exemplary lower pressure limits are 1, 10, 20, and 30 MPa (0.15,1.45, 2.9, 4.35 kpsi, respectively). Exemplary upper pressure limits are1500, 1000, 500, 300, 250, and 200 MPa (217, 145, 72.5, 43.5, 36.3, and29 kpsi, respectively).

In certain embodiments, polymerization is performed in a supercriticalpolymerization system. In such embodiments, the reaction pressure isabove the critical the pressure of the polymerization system. In someembodiments, some or all reactors operate at homogeneous supercriticalpolymerization conditions The supercritical polymerization process ofthe in-line blending processes disclosed herein may be carried out atthe following pressures. In one embodiment, the pressure is no lowerthan the crystallization phase transition pressure of thepolymer-containing and plasticizer containing fluid reaction medium atthe reactor temperature or no lower than 10, or 5, or 1, or 0.1, or 0.01MPa below the cloud point of the fluid reaction medium at the reactortemperature. In another embodiment, the pressure is between 10 and 500MPa, between 10 and 300 MPa, or between 20 and 250 MPa. In one form, thepressure is above 10, 20, or 30 MPa. In another form, the pressure isbelow 1500, 500, 300, 250, or 200 MPa. In another form, the cloud pointpressure is between 10 and 500 MPa, between 10 and 300 MPa, or between20 and 250 MPa. In yet another form, the cloud point pressure is above10, 20; or 30 MPa. In still yet another form, the cloud point pressureis below 1500, 500, 300, 250, or 200 MPa.

Total Monomer Conversion for Homogeneous Fluid Phase Reactions:

Increasing the conversion of the total monomer feed in a single-pass inthe individual reactor trains of the parallel reactor bank can reducethe monomer recycle ratio thus can reduce the cost of monomer recycle.Increasing monomer recycle ratios (i.e., the ratio of recycled/totalmonomer feed to the reactor train) require the treatment and recycle oflarger monomer volumes per unit polymer production, which increasesproduction cost. Therefore, higher monomer conversion (lower recycleratios) often provides for improved process economics. However, becausehigh polymer content in the polymerization system, particularly inhomogeneous polymerization systems, yields high viscosities, whichcorrespondingly may make reactor mixing, heat transfer, and downstreamproduct handling difficult, the monomer conversion in a single pass haspractical operation limits. The viscosity of monomer-polymer blends andthus the practical conversion limits can be readily established bystandard engineering methods known in the art (M. Kinzl, G. Luft, R.Horst, B. A. Wolf, J. Rheol. 47 (2003) 869). Single-pass conversionsalso depend on operating conditions and product properties. For example,FIG. 4 shows how increasing conversion reduces the polymer molecularweight. Therefore, monomer conversion may also be constrained by thedesire to increase the molecular weight of the blend component made inthe given reactor train, particularly in the reactor trains producingthe high molecular weight base polymer in-line blending components.Exemplary, but not limiting, total monomer single pass conversions arebelow 90%, more particularly below 80% and still more particularly below60%. Total monomer conversion is defined as the weight of polymer orplasticizer made in a reactor or in a reactor train divided by thecombined weight of monomers and comonomers in the feed to the reactor orreactor train. It should be understood that while high total monomerconversion is often limited by product viscosity or by product propertytargets, the conversion of some highly reactive monomer componentspresent in some monomer feed blends may be higher than 90%. For example,the single-pass conversion of ethylene in ethylene-propylene or inethylene-higher olefin feed blends may be nearly complete (approaching100%) and is disclosed herein.

As mentioned above, another factor limiting the total monomer conversionis the MW-decreasing effect of conversion (see FIG. 4). Therefore, theproduction of the base polymer blend components with high MW requiresthe moderation of monomer conversion in a single pass beyond that ofwhat viscosity and other practical operation considerations woulddictate. Hence, for the production of base polymer blend components withhigh molecular weight (particularly those with higher than >200 kg/molweight-averaged molecular weight—M_(w)), the total monomer conversionmay need to be below 30%. Again, the conversion of some highly reactivecomponents in a monomer feed blend may be higher, and may even approach100%.

The single-pass conversion in the reactors disclosed herein may beadjusted by the combination of catalyst concentration and total feedflow rate. The total feed rate determines the average residence time (ina back-mixed reactor equal to the reactor volume divided by the totalvolumetric flow rate of the effluent). The same conversion may beachieved at lower residence time by increasing the catalystconcentration in the feed and vice versa. Lower catalyst concentrationmay reduce catalyst cost, but may also reduce volumetric productivitythus requiring higher residence times, and ultimately a larger reactorand thus higher investment cost for the same polymer productioncapacity. The optimum balance between residence time/reactor volumes andcatalyst concentration may be determined by standard engineering methodsknown in the art. A wide-range of polymer and plasticizer blendcomponents may be produced in the reactors disclosed herein at reactorresidence times ranging from 1 sec to 120 min, particularly from 1 secto 60 min, more particularly from 5 sec to 30 min, still moreparticularly from 30 sec to 30 min, and yet still more particularly from1 min to 30 min. In yet another form of the in-line blending processembodiments disclosed herein, the residence time in the reactorsdisclosed herein may be less than 120, or less than 60, or less than 30,or less than 20, or less than 10, or less than 5, or less than 1minute(s).

In certain embodiments, one or more of the polymer blend componentand/or one or more of the plasticizer blend component reactor trains ofthe in-line blending process disclosed herein operate at supercriticalconditions advantageously at homogeneous supercritical conditions, ormore advantageously at bulk homogeneous supercritical conditions. Theresidence times in the supercritical polymerization reactors,particularly in the bulk homogeneous supercritical reactors disclosedherein are generally lower than the residence times in solution, gasphase, and slurry processes due to the high reaction rates achieved atthe conditions of the supercritical polymerization process. In-lineblending processes disclosed herein applying bulk homogeneoussupercritical polymerizaton often choose residence times between 1 and60 min, and more particularly between 1 and 30 min.

The reactors in the individual trains and in the entire bank can be ofany type useful for making polymers (for a review of differentpolymerization reactors see Reactor Technology by B. L. Tanny in theENCYCLOPEDIA OF POLYMER SCI. AND ENG., Vol. 14, H. F. Mark et al., Eds.,Wiley, New York, 1988, and J. B. P. Soares, L. C. Simon in the HANDBOOKOF POLYMER REACTION ENGINEERING, T. Meyer and J. Keurentjes, Eds.,Wiley-VCH, Weinheim, 2005, p. 365-430.) and can be constructed the sameway or can be different. The optimal reactor type and configuration canbe determined by standard techniques well known in the art of polymerreactor engineering.

It should be recognized that the catalytic activity and thus thevolumetric productivity in the individual reactors may be different. Ifthe reactor effluents for in-line blending are directly blended, thecatalytic activity and the volumetric productivity may determine thereactor sizes required for the production of the individual polymer andplasticizer blend components. In order to reduce cost, a single plantmay need to produce several plasticized polymer blends with differentpolymer and plasticizer components blended over a range of blend ratios.Consequently, a parallel reactor bank will often have reactors ofdifferent sizes allowing for a flexible and thus more cost effectiveconfiguration for the production of different plasticized polymer blendgrades. The optimal reactor volumes may be determined from thecombination of the composition of the target plasticized polymer blendsand the volumetric reactor productivity data using optimization methodsknown in the art of chemical engineering.

In commercial practice, reactor productivity tends to vary to somedegree, which in turn may lead to the corresponding level of variabilityin polymer-plasticizer blend ratios. In one embodiment, buffer tanks maybe added to the process downstream of the reactors comprising the bankof parallel reactors, but before the polymer-plasticizer mixing orblending point to compensate for the fluctuations of the volumetricproductivity in each reactor train producing the individual polymer andplasticizer blend components (see for example FIG. 8). The buffer tanksmay improve the compositional control of the final product blends byhomogenizing the individual reactor effluents and by allowing a moreindependent metering of the plasticized polymer blend components. Whenan individual reactor train effluent is stored in the buffer tank in itsliquid state at a pressure below its bubble point, essentially theentire volume of the buffer tank is available for compensating for thedifferences in the blending and production rates. However, when theindividual reactor effluent is stored in the buffer tank in itssupercritical state or in its liquid state but at pressures above itsbubble point, the dense liquid or supercritical fluid fills the entiretank. In such operation modes, the buffering capacity, i.e. the capacityto deviate from the instant reactor flow rate, is more limited and isassociated with the pressure/density changes allowed in the buffer tankand with the size of the buffer tank. In the latter case, the processstreams may be driven by a gradual pressure drop downstream of thereactor to avoid the cost of installing and operating booster pumps.However, booster pumps may be alternatively installed and operatedwithin the process to increase the pressure range and thus the bufferingcapacity of the system. When no booster pumps are deployed, the pressureof the buffer tank should be lower than that of the reactor, but higherthan that of the lines downstream of the blending point.

Apparently, while feasible, controlling this kind of buffer system isdifficult and it is not very efficient. Thus, in another embodiment,when the individual reactor effluent is stored in the buffer tank in itssupercritical state or in its liquid state but at pressures above itsbubble point, the conditions in the buffer tanks may be set to achievefluid-fluid phase separation (separator-buffer tank operation).Buffering in this mode can be achieved by allowing the fluid level ofthe denser polymer-rich and/or plasticizer-rich phase to move up anddown between the minimum and maximum levels allowed for the desiredlevel of separation while taking the monomer-rich upper phase out of theseparator buffer via a pressure control valve. One skilled in the artcan see that this operation mode is analogous to the operation of abuffer tank filled with a liquid phase containing the polymeric orplasticizer product and a vapor phase containing the more volatilecomponents, such as monomer(s) and solvent(s). In the supercriticalregime, the upper phase is a monomer-rich supercritical fluid, while thelower phase is a polymer-rich or plasticizer-rich supercritical fluid,the latter of which can be withdrawn for blending at a controlled raterequired for is making a constant blend ratio, independent of theshort-term fluctuations in the production ratios of the individual blendcomponents. A similar analogy may be derived for liquid-filledoperations. The polymer or plasticizer content, and thus the viscosityof the polymer-rich or plasticizer-rich phase can be controlled byproperly adjusting the temperature at constant pressure or by adjustingthe pressure at constant temperature in the separator-buffer tank(s). Inthis embodiment, the polymer-rich and/or plasticizer-rich effluent(s) ofthe separator-buffer tank(s) are combined with the direct, unseparatedeffluent of one of the reactor trains upstream of the separator-blendingvessel that recovers the monomer of the direct reactor effluent as asupernatant and the in-line plasticized polymer blend as the bottomphase. In this particular embodiment, one of the separators serves as aseparator-blender, while the rest of the separators serve asseparator-buffers. Advantageously, the separator-blender is connected toa reactor train making a polymer blending component while theseparator-buffer vessels are connected to a plasticizer train. Thisconfiguration allows the recovery and recycle of a significant portionof plasticizer monomer without the need for separation from monomer fromthe polymer train.

As described before, certain embodiments recover the one or more in-lineproduced plasticizer blend components in their essentially pure liquidform before blending them with streams comprising the one or more highmolecular weight base polymer components. In these embodiments, thedisclosed processes may employ one or more storage tanks for storing andbuffering the plasticizer blend components to increase blendingflexibility and to improve composition control. These embodiments mayinclude plasticizer export from the disclosed in-line blending plantsfurther increasing their versatility and the value they may offer.

In another embodiment of the processes disclosed herein, polymeradditives may be added to the in-line-produced plasticized polymerblends at ratios of up to 40 wt %, or up to 30 wt %, or up to 20 wt %,or up to 10 wt %, or up to 5 wt % to further improve product quality andproduct properties. Exemplary, but not limiting polymer additives,include specialty polymers including polar polymers, waxes,antioxidants, clarifiers, slip agents, flame retardants, heat and uvstabilizers, antiblocking agents, fillers, reinforcing fibers,antistatic agents, lubricating agents, coloring agents, foaming agents,tackifiers, organically modified clays such as are available fromSouthern Clay, etc. and masterbatches containing the above components.Hence, one or more polymer additive storage tanks containing liquid,molten, dissolved, or dispersed polymer components and polymer additivesmay be added to the processes disclosed herein. If solvent(s) is used inthese polymer additive storage tanks, it may be advantageously the sameas used in the polymerization and plasticizer reactors previouslydescribed in order to avoid an increase in separation costs in thesolvent recovery and recycle section of the process. For example, whenthe polymer synthesis process is performed in supercritical propylene,the off-line produced polymer additives may also be advantageouslydissolved in supercritical propylene. However, other solvent(s) orsolvent-free introduction may be used with the polymer additives.Solvent-free introduction of the polymer additive components may be usedwhen the additive component is brought into its molten state or when theadditive component is a liquid at ambient temperatures.

The homogeneous supercritical polymerization and the solutionpolymerization processes are particularly suitable for providing boththe product base polymer component(s) and the plasticizer component(s)of the plasticized polymer blend in a dissolved fluid state. In oneparticular embodiment, the supercritical polymerization process isperformed in the substantial absence of an inert solvent/diluent (bulkhomogeneous supercritical polymerization) and provides the product in adissolved supercritical state for the downstream in-lineseparation-blending process. More particularly, the supercriticalpolymerization of propylene is performed in the substantial absence ofan inert solvent/diluent (bulk homogeneous supercritical propylenepolymerization) and provides the product in a dissolved supercriticalstate for the downstream in-line separation-blending process.

The total amount of inert solvents is generally not more than 80 wt % inthe reactor feeds of the polymer and plasticizer reactor trains. In someembodiments, where the feed essentially comprises the monomer or monomerblend, like for example, bulk slurry, or bulk supercritical, or bulksolution polymerizations, the minimization of solvent use is desired toreduce the cost of monomer recycling. In these cases, the typicalsolvent concentration in the reactor feed is often below 40 wt %, orbelow 30 wt %, or below 20 wt %, or below 10 wt %, or below 5 wt % oreven below 1 wt %. In one form disclosed herein, the polymerizationsystem of the polymer and plasticizer reactor trains comprise less than20 wt % aromatic hydrocarbons and advantageously less than 20 wt %toluene. In another form disclosed herein, the polymerization system ofthe polymer and plasticizer reactor trains comprise less than 40 wt %saturated aliphatic hydrocarbons and advantageously less than 40 wt % ofhexanes, or pentanes, or butanes, and propane, or their mixtures.

Fluid Phase In-Line Blending Process Configuration:

The disclosed fluid phase in-line blending processes for makingin-line-plasticized polyolefins may have different detailed processconfigurations. For example, the number of parallel reactor trains andtheir configurations in the parallel reactor bank may be varied.Typically, each reactor train serves to produce a single in-line polymeror plasticizer blend component. A given train of the parallel reactorbank may be configured as a single reactor or two or more reactors inseries. From a practical commercial plant design standpoint, however,there should be a minimum number of reactors for a given train of theparallel reactor bank in order to make a given polymer or plasticizerblend component. Generally, not more than ten series reactors areutilized and more particularly not more than three series reactors aregenerally utilized in a given reactor train. The number of paralleltrains in the parallel reactor bank may be two, three, four or five ormore. The number of reactors in the parallel reactor bank may be anynumber, although for economic reasons the number of reactors should bemaintained as low as the desired product grade slate and plant capacityallows. The optimum number of parallel reactor trains (also referred toas legs of the reactor bank) may be determined by standard chemicalengineering optimization methods well known in the art. Most typically,the polymerization-blending plant will have two or three parallelpolymerization reactor trains or legs in the reactor bank producingproduct blends with the corresponding number of in-line polymer blendcomponents. However, more than three parallel reactors/legs may beemployed if the production of the target product blends so requires.Besides the in-line base polymer and plasticizer blend components, thefinal plasticized polymer blends often contain additives and modifiersthat are not produced within the same polymerization process. Therefore,it should be understood that the number of components in the finalproduct blend typically is higher than the number of reactor trains orthe number of in-line plasticized polymer blend components.

Based on the source of the in-line blend components, the disclosedin-line blending processes producing in-line-plasticized polyolefins maybe grouped into three options: (1) all plasticizer blending componentsproduced in-line, i.e., in the reactor bank of the in-line blendingprocess, (2) one or more plasticizer blending components producedin-line and one or more additional plasticizer blending componentsproduced off-line, and (3) all plasticizer blending components producedoff-line. Furthermore, the processes falling under options (1) and (2),may deliver the one or more in-line-produced plasticizer blendcomponents to the blending point with the base polymer containing stream(a) without removing any of the light components from the one or moreplasticizer reactor effluents, such as the unreacted monomers andoptional inert solvents/diluents (unreduced reactor effluent), (b) afterpartial recovery of the said light components from the said one or moreplasticizer-containing reactor effluents (reduced reactor effluent), and(c) after full recovery of the essentially pure plasticizer blendingcomponent, i.e., after removing essentially all of the said lightcomponents from the said plasticizer-containing one or more reactoreffluents (fully recovered plasticizer). As stated before, theplasticized polyolefin product may contain one or more high molecularweight base polymer components for options (1) and (2), and may containtwo or more high molecular weight base polymer components for option(3).

The fluid phase in-line blending processes disclosed herein may alsooptionally incorporate other polymers, other plasticizers and otherpolymer additives that were produced outside the reactor bank of theprocesses disclosed herein. The optional other polymer, otherplasticizer, and polymer additive components may first be transferredinto solution or molten fluid state before being blended with thein-line produced polymer and plasticizer blend components. These otherpolymer, other plasticizer, and polymer additive components may bestored in polymer additive storage tanks containing liquid, molten, ordissolved polymer components, plasticizer components and polymeradditives prior to being transferred and metered to theseparation-blending vessel or to a mixing point upstream or downstreamof the separation-blending vessel. Other polymer, other plasticizer, andpolymer additive components may be accurately metered to the blendingvessel or to another mixing point by one or more pumps or if thedownstream pressure is lower, through the use of one or more pressureletdown valves. The optional other polymer, other plasticizer, andpolymer additives and modifiers can be mixed into the product upstreamof or directly in the separator-blending vessel or downstream of theseparator-blending vessel of the processes disclosed herein. In order tosimplify monomer treatment in the monomer recycle train and thus toreduce the cost of monomer recycle, it may be advantageous to add theother polymer, other plasticizer and polymer additives and modifiersdownstream of the separator-blending vessel. In such embodiments, theadditives and modifiers may be mixed with the in-line producedplasticized polymer blend in dedicated pieces of equipment or in thehardware of the product finishing section of the processes disclosedherein, for example, in a low-pressure separator or in a devolatizerextruder.

Referring to FIG. 6, in one exemplary embodiment of the fluid phasein-line blending process disclosed herein, the effluents of all parallelreactor trains in the reactor bank are brought into a singlehigh-pressure separator-blending vessel (also referred to asseparator-blender or high-pressure separator). One or more of theparallel reactor trains produce polymer blend components and optionally(as in options (1) and (2) described earlier) one or more of theparallel reactor trains produce plasticizer blend components. Theseparator-blender separates some or most of the low molecular weightcomponents, such as monomer(s), optional solvent(s), and product lights(monomer-rich phase) from the (monomer-lean) polymer-rich phase, butalso blends the polymeric and optional plasticizer blend components madein different reactor trains of the in-line process forming apolymer-rich blend effluent that also comprise the optional in-lineproduced plasticizer. In some embodiments (not shown in FIG. 6), one ormore off-line-produced plasticizers may also be blended at the samepoint of the process, i.e., in which case the polymer-rich blendeffluent will also carry the one or more off-line-produced plasticizerblend components. This mode is also referred to as single separationvessel operation even if the process employs one or more low-pressureseparators. The number of reactor trains in the parallel bank may be 2,3, 4, and up to n. The effluents of the different reactor trains andthus the individual polymer and the optionally in-line-producedplasticizer blend components are combined upstream of the separationvessel after individual pressure let down valves, which function tobring the reactor train effluents to the common pressure of theseparator-blending vessel. Catalyst killing agent(s), may be optionallyintroduced prior to or into the separator-blending vessel to minimizefurther polymerization outside the polymerization reactors. Optionally,one or more static mixers positioned before the separator-blendingvessel, but downstream of the mixing point, may also be utilized toenhance mixing between the reactor train effluents. Optionally, some orall reactor train effluents may be heated before the pressure letdown(not shown in FIG. 6) in order to maintain the temperature in thedownstream lines and in the separation-blending vessel at the desiredvalue, i.e., above the solid-fluid phase transition temperature of thepolymer-rich phase and plasticizer-rich phase of the separator-blender,but below the cloud point of the combined effluents entering theseparator-blending vessel to allow the formation of a plasticizedpolymer-rich denser fluid phase and a monomer-rich lighter fluid phase.

After the combined reactor train effluent streams enter theseparator-blending vessel, monomer recycle (monomer-rich phase) emergesfrom the top of the separator-blending vessel and an optionallyplasticized (as in the aforementioned options (1) and (2) and whenoptional off-line-produced plasticizers introduced) polymer-rich blendemerges from the bottom of the vessel. The optionally plasticizedpolymer-rich blend may then be conveyed to a downstream finishing stagefor further monomer stripping, drying and/or pelletizing. As describedearlier, modifiers and additives (i.e. other polymers, otherplasticizers, and polymer additives) may also be introduced eitherbefore or into the separator-blending vessel or downstream of it.However, a downstream introduction of these modifiers and additivestypically simplifies monomer recycle, and is thus advantageous. In thisembodiment, the single separator-blending vessel serves as both aseparator and a blender. One advantage of this exemplary embodiment isthe utilization of a single separator-blending vessel, which providesfor process simplicity because it functions for both separation andblending purposes. One disadvantage of this exemplary embodiment is thatbecause all reactor train effluent streams are combined, the recoveredmonomer stream from the separator-blending vessel may need to beseparated prior to recycle to the individual reactor trains in the bankof parallel reactors. In summary, this embodiment may be simpler andthus lower cost in the separator section, but may be more costly in themonomer separation and recycling loop section of the process.

FIG. 7 depicts an alternative exemplary embodiment of the fluid phasein-line blending process disclosed herein in which each reactor trainhas a dedicated separator vessel with the exception of one reactoreffluent train where all polymer-rich and the optional plasticizer-richphases (as in the aforementioned options (1) and (2)) from the otherreactors are combined in a high-pressure separator that also serves as ablending vessel (also referred to as multiple separation vesseloperation). In this embodiment, for all but one of the reactor trains(all but train n in FIG. 7), the single-stream high-pressure separatorserves as a separator to separate a polymer-enriched phase orplasticizer-enriched phase from a monomer-rich phase in the reactoreffluent stream. In order to keep the content of low molecular weightcomponents higher and thus to keep the viscosity of the optionallyplasticized polymer-enriched phase lower, the single-streamhigh-pressure separators dedicated to the individual reactor trainsoften operate at a somewhat higher pressure than the one downstreamhigh-pressure separator that serves both as a separator and as a blender(separator-blender). Therefore, there is an optional pressure letdownbetween these separators and the separator-blender. For the onehigh-pressure separator (separator-blender) where the other polymer-richphases and plasticizer-rich phases are combined and the reactor traineffluent from one of the reactor trains is introduced (reactor train nin FIG. 7), the separator serves both product blending and product-feedseparating functions. Catalyst killing agent may be optionallyintroduced prior to or into each separator vessel, including theseparator-blender to minimize further polymerization outside thepolymerization reactors. One or more off-line-produced plasticizers, andother additives may optionally also be blended in at the same mixingpoint (not shown in FIG. 7). Optionally, one or more static mixerspositioned before the separator-blending vessel, but downstream of themixing point may be utilized to enhance mixing between the polymer-richphases, the optional plasticizer-rich phases of the reactor trains, theoptional off-line-produced plasticizers and other optional additives,and the reactor train effluent of the reactor train associated with theseparator-blender. Optionally, some or all reactor train effluents maybe heated before the first pressure letdown (not shown in FIG. 7) inorder to maintain the temperature in the downstream lines and in theseparators, including the separation-blending vessel, at the desiredvalue, i.e., above the solid-fluid phase transition temperatures of thepolymer-rich phases and plasticizer-rich phases but below the cloudpoint of the streams entering the separators, including theseparator-blender, to allow the formation of plasticized polymer-richdenser fluid phase and monomer-rich lighter fluid phase. The optionaloff-line-produced plasticizer and other optional additive feed streamsmay also be heated before their introduction for the same purpose. Theprocess of this embodiment may be advantageous in the production ofplasticized polymer blends that include one or more in-line-producedplasticizers and one or more high molecular weight polymers. In thisembodiment, the plasticizer train(s) has/have its (their) ownseparator(s) and the polymerization train to produce a high molecularweight polyolefin serves as a blender. The process of this embodimentmay also be advantageous in the production of plasticized polymer blendsthat include different homopolymers or homopolymer(s) and copolymer(s)as blend components. In this embodiment, the homopolymerization train(s)and the plasticizer train(s) has/have its (their) own separator(s) andthe copolymerization train (or one of the copolymerization trains incase of more than one copolymer trains used) serves as a blender. Themonomer(s) recovered in the separator(s) dedicated to individual reactortrain(s) may be recycled to the corresponding reactor train(s) withoutthe complex separation from other monomers as was associated with singleseparation-blending vessel operation previously described. Hence, oneadvantage of this embodiment is that monomer recycle is simplified andthus affords lower cost in the monomer recycle loop. While multipleseparation vessel operation increases cost in the separator section, itadds flexibility in the monomer recycle loops. In summary, thisembodiment may be more complicated and higher cost in the separatorsection, but may be simpler in the monomer recycle loops.

In one particular embodiment similar to the process scheme depicted inFIG. 7, one or more of the in-line-produced plasticizers may be fullyrecovered in their essentially pure form before blending them with theeffluent streams carrying the one or more high molecular weight basepolymer in-line blending components. The full recovery of the one ormore plasticizer blend components may include one or more fluid-fluidphase separation, or distillative separations comprising one or moreliquid-vapor equilibrium conditions, and any combination thereof. Theoperation of fluid-fluid phase separators is disclosed in details inU.S. Patent Application No. 60/876,193 filed on Dec. 20, 2006, hereinincorporated by reference in its entirety. Distillative separationscomprising one or more liquid-vapor equilibrium conditions employingflash drums, knock-out pots, or distillation columns, or vacuumstripping, etc., are well-known in the art of chemical engineering. Thefull recovery of the in-line-produced plasticizer blending component maybe advantageous when in-line-produced plasticizer blending component isa liquid at ambient temperature and/or when some fraction of it isexported from the in-line blending plant disclosed herein sinceplasticizer liquids readily blend with the process streams comprisingthe high molecular weight base polymer. Further advantages may arisefrom the full recovery of one or more in-line-produced plasticizersbefore blending them with the effluent streams carrying the one or morehigh molecular weight base polymer in-line blending components when thecombined monomer pool of the one or more optional plasticizer reactortrains has no common monomer members with the combined monomer pools ofthe reactor trains producing the high molecular weight base polymerin-line blending components.

Since both embodiments of FIGS. 6 and 7 serve the same function ofproduct blending and separation of the polymer-rich and plasticizer-richphases from the monomer-rich phases, the choice between them is drivenby the economics of a given plant producing a given product slate andmay be determined by standard engineering optimization techniques knownin the art.

FIG. 8 presents another alternative exemplary embodiment of the fluidphase in-line blending process disclosed herein in which is provided adedicated buffer tank in which no phase separation occurs for eachreactor train and in which the reactor train effluents are combined in asingle separator-blending vessel (also referred to as single separationvessel operation with buffer tanks). Each of the n parallel reactortrains in the reactor bank is provided with its own buffer tank toenable the fine-tuning of the mixing ratio of the polymer andplasticizer blend components. Pressure let down valves may be positionedon the inlet and outlet side of each buffer tank to control the in-linepolymer or plasticizer blend component flow. Optionally, the reactoreffluents may be heated to maintain the desired temperature in thedownstream separator-blender as described above. Catalyst killing agentmay be optionally introduced prior to or into each buffer tank tominimize further polymerization outside the polymerization reactors.Optionally, one or more static mixers positioned after the mixing pointbut before the separation vessel for blending may be utilized to enhancemixing between the reactor effluents being fed from the buffer tanks. Incomparison to the single separation vessel operation of FIG. 6, thisalternative exemplary embodiment allows for more precise control of theblend ratio and quality but without the benefit of dedicated monomerrecovery provided by the configuration depicted in FIG. 7. As previouslydiscussed, this embodiment may improve the control of product blendratio and hence product quality, but its buffer capacity may be limited,particularly when the reactor effluent is in its supercritical state orwhen its pressure is above its bubble point.

An alternative design employing buffering capability is depicted in FIG.9. FIG. 9, a variation of the multiple separation vessel operationdepicted in FIG. 7, and an advantageous version of the buffer-onlyoperation shown in FIG. 8, presents yet another alternative exemplaryembodiment of the fluid phase in-line blending process disclosed herein.In this exemplary embodiment the single-stream high-pressure separatorsdedicated to the individual reactor trains also serve as buffer tanks.Referring to FIG. 9, for all reactor trains but n, the reactor traineffluent is fed to a dual-purpose separator-buffer for both separationof the polymer-rich phase or plasticizer-rich phase from the supernatantmonomer-rich phase and storage of polymer-rich phase or the optionalplasticizer-rich phase prior to conveyance to a downstream blendingseparator. These single-stream separators dedicated to individualreactor trains afford buffering by allowing the level of the denserpolymer-rich and plasticizer-rich phases to move between an upper and alower limit. This buffer capacity allows for the correction in thepotential fluctuations in the production rates of the individual in-lineblend components and thus provides a means for a more precise control ofthe polymer-plasticizer blend ratio. For reactor train n, thehigh-pressure separator (separator-blender) functions to separate thepolymer-rich phase from the monomer-rich phase for the reactor effluentfrom reactor n and also to blend the polymer-rich phases andplasticizer-rich phases from all reactors (1, 2, through n in FIG. 9).From a blend control point of view, there is no buffering for thein-line component n, and thus all other blend component flows to theseparator-blending vessel, and ultimately their production rates, arecontrolled by the production rate in reactor train n in order tomaintain the desired blend ratios. Catalyst killing agent may beoptionally introduced prior to or into each separator vessel to minimizefurther polymerization within the separator. Optionally, one or morestatic mixers positioned before the separation vessel for blending maybe utilized to enhance mixing between polymer-rich phases of thereactors and the reactor effluent of the reactor associated with theblending separator. For heat and pressure management, the sameconsiderations, configurations, and controls may be applied as describedfor the previous embodiments. As in all process configurations, optionalmodifiers and additives may be introduced either prior or into theseparator-blending vessel or downstream of it.

FIG. 10 presents yet another exemplary embodiment of the fluid-phasein-line blending process disclosed herein in which one of the parallelpolymerization trains (train 1 in FIG. 10) produces a high molecularweight base polymer blending component in the form of solid pellets,i.e. operates in the slurry polymerization regime. Thus in order tobring the polymer into a dissolved state before in-line blending, thereactor effluent is brought into a heated stirred vessel. In order tokeep the entire reactor effluent in a dense fluid phase, the pressure ofthe reactor effluent is increased by a slurry pump. Slurrypolymerization typically operates at lower temperatures thansupercritical and solution polymerizations and thus may afford productswith higher molecular weight and melting peak temperatures, which mayprovide advantages in certain plasticized polymer blend applications.However, the dissolution of polymer pellets adds cost and tends to beprone to fouling and other operational issues. Other aspects of thein-line blending process disclosed herein, such as catalyst killing,additive blending, heat and pressure management, as described in thepreviously described embodiments, apply hereto as well.

FIG. 11 presents still yet another exemplary embodiment of the fluidphase in-line blending process disclosed herein in which one or moreoptional polymer, and/or plasticizer, and/or other polymer additivestorage tanks may be added to the process for the storage and meteringof other fluid polymers and polymer additives to the blending vessel.Optional pump(s) may be used to convey the one or more polymers,plasticizers or other polymer additives to the separator vessel forblending. Note that FIG. 11 presents the particular embodiment whereinthe one or more optional polymer, and/or plasticizer, and/or morepolymer additive storage tanks are added to the singleseparation-blending vessel operation with buffer tanks configuration ofFIG. 8. However, the one or more optional polymer, and/or plasticizer,and/or one or more polymer additive storage tanks may be added to theprocesses depicted in FIG. 6, FIG. 7, and/or FIG. 9 without deviatingfrom the spirit of the fluid phase in-line blending process disclosedherein. Similarly, optional off-line produced polymers, plasticizers,modifiers, and additives may be introduced in any part of the polymerfinishing section or in a dedicated section prior to the productfinishing section of the process disclosed herein. Other aspects of thein-line blending process disclosed herein, such as catalyst killing,additive blending, heat and pressure management, as described in thepreviously described embodiments, apply hereto as well.

As will be appreciated by one skilled in the art of chemicalengineering, the process schematic details of the design of the fluidphase in-line blending process in terms of reactor configuration,separator configuration, valving, heat management, etc. may be setdifferently without deviating from the spirit of the fluid-phase in-lineblending process disclosed herein. The choice between differentembodiments of the processes disclosed herein will be driven by productperformance requirements and process economics, which can be readilydetermined by standard engineering techniques. However, the in-lineblending processes disclosed herein are advantageous relative to theprior art by the virtue of reduced blending cost due to savings ininvestment and operation costs, and enabling well-controlled andcost-effective molecular-level blending to yield enhanced plasticizedpolymer blend performance.

The processes disclosed herein provide an effective recycle pathway formonomer separation from the products. They are particularly advantageousin homogeneous olefin polymerization processes such as, for example,bulk homogeneous supercritical propylene polymerization (SCPP), solutionpolymerization, and bulk solution polymerization. As will be discussedin more detail below for bulk homogeneous polymerization processes, theefficient separation of monomer and polymer is achieved byadvantageously utilizing the cloud point pressure and temperaturerelationships for the relevant (polymer/olefinic monomer) or(copolymer/olefinic monomer blend); e.g. (polypropylene/propylenemonomer), (ethylene-propylene copolymer/ethylene-propylene monomerblend), etc. mixtures.

For illustration, cloud point curves are shown in FIGS. 13-22 for threedifferent polypropylene samples having different molecular weights andcrystallinities dissolved in propylene (at 18 wt %). (Achieve 1635 PP isa commercially available metallocene-catalyzed isotactic polypropylenehaving a Melt Flow Rate, MFR, (I₁₀/I₂-ASTM 1238, 230° C., 2.16 kg) of 32g/10 min available from ExxonMobil Chemical Company, Houston, Tex.ESCORENE PP 4062 is a commercially available isotactic polypropylenehaving an MFR of 3.7 g/10 mm, available from ExxonMobil ChemicalCompany, Houston, Tex. PP 45379 is an isotactic polypropylene having anMFR of 300 g/10 min produced using a supported metallocene in a slurrypolymerization process.

Plasticized Polymer Blend Formulations and Products:

Many different types of plasticized polymer blends may be made by thefluid-phase in-line blending process disclosed herein. A major fractionof a blend is defined as 50% or more by weight of the blend. A minorfraction of a blend is defined as less than 50% by weight of the blend.The plasticized polymer blend formulation produced by the in-lineprocesses disclosed herein generally include a major fraction of one ormore high molecular weight polymer components and a minor fraction ofone or more plasticizers.

Besides achieving plasticization, i.e., increasing softness and/or coldtemperature flexibility and/or processability, etc., by in-line blendingof plasticizers, plasticized polymer blends produced by the fluid phasein-line blending process disclosed herein may also be used to blend basepolymer components and thus, for example, to provide bi- ormulti-modality to the distributions of the molecular characteristics ofresins encompassed herein. Non-limiting examples of such materials areblends with similar polymer components, but having different molecularweights, different levels of incorporation of comonomers, differentlevels of molecular defects like stereo- and regio-defects, and thelike. The result of such bimodality is to produce an improved suite ofproperties in the blend as compared to any of the polymer componentsalone. Processing ease and melt strength may be improved by suchblending as well as the balance between stiffness-toughness, heatresistance, tolerance of exposure to high energy radiation and otherproperties of the resins.

The weight fractions of the individual base polymer components in theblends made by the fluid phase in-line blending process disclosed hereinmay be similar or different. The polymer blends disclosed herein mayalso derive similar improvements from combinations of differentmaterials in similar or different proportions. One non-limiting exampleof a useful polymer blend made by the fluid phase in-line blendingprocess disclosed herein includes a major fraction of a highlycrystalline moderate molecular weight polymer and a minor fraction of avery high molecular weight, elastomeric polymer with low or no inherentcrystallinity. Another non-limiting example of a useful polymer blendmade by the fluid phase in-line blending process disclosed hereinincludes a major fraction of a soft, tough, low melting polymer with aminor fraction of a highly crystalline, high melting polymer. Stillanother non-limiting example of a useful polymer blend made by the fluidphase in-line blending process disclosed herein includes a majorfraction of a highly crystalline polymer with a minor fraction of a lowor non-crystalline polymer where the low or non-crystalline polymer isnon-elastomeric. This example also encompasses plasticized polymerblends.

The plasticized polymer blends made by the fluid phase in-line blendingprocess disclosed herein provide for improved properties, and hence usein a wide array of applications. One such exemplary, but non-limitingapplication, is in medical applications requiring improved resistance tosterilizing doses of high-energy radiation. A polymer blend useful forthis particular application may include from 75 to 99 wt % moderatemolecular weight propylene homopolymer with 1 to 25 wt % of an ethyleneplastomer, which acts as a plasticizing component. Alternatively, theethylene plastomer may be replaced by a propylene-ethylene copolymercontaining from 8-16 wt % ethylene, which also acts as a plasticizingcomponent. The plastomer or high propylene copolymer component of theblend provides superior initial ductility as well as retention ofductility and tolerance of the sterilizing radiation to the blend whilethe homopolymer component imparts excellent strength, stiffness andresistance to deformation at elevated temperature to the blend. Polymerblends of propylene homopolymer and ethylene plastomer orpropylene-ethylene copolymer are generally clearer or nearly as clear asthe unblended propylene homopolymer component.

Another exemplary, but non-limiting application of where the plasticizedpolymer blends made by the fluid phase in-line blending processdisclosed herein find application is in various conversion processes. Inparticular, by combining high and low molecular weight propylenepolymers in either similar or different proportion, the molecular weightdistribution of the blend may be significantly broader than of eitherindividual component. The ratio for blending the high and low molecularweight propylene polymers depends upon the desired final melt flow rateand molecular weight distribution. Such broader molecular weightdistribution polymers are easier to extrusion blow mold, blow into film,thermoform, orient into film, and stretch blow mold than narrowermolecular weight distribution polymers. Optionally, one of the polymercomponents can have long chain branching introduced through addition ofa small quantity of alpha-omega-diene.

Still another exemplary, but non-limiting application of where theplasticized polymer blends made by the fluid phase in-line blendingprocess disclosed herein find application is in devices and packagingmaterials requiring good impact resistance, and particularly in lowtemperature environments. Plasticized polymer blends useful for thisparticular application may include from 80 to 99 wt % of a propyleneimpact copolymer (a blend of high crystallinity propylene homopolymerand low crystallinity propylene-ethylene copolymer) and 1-20 wt % ofplasticizer.

In applications requiring clarity, incorporating into the plasticizedpolymer blend a minor fraction of a highly compatible ethylene plastomeror propylene copolymer known to have a minimal deleterious effect oreven a positive effect on the clarity of blends with polypropylene mayprovide for such. Such plastomers comprise those with a refractive indexand viscosity similar to the polypropylene with which they are to beblended. Compatible propylene copolymers are exemplified bypropylene-ethylene copolymers containing less than 16 wt %, or less than11 wt %, or less than 6 wt % ethylene.

Still yet another exemplary, but non-limiting application of where theplasticized polymer blends made by the fluid phase in-line blendingprocess disclosed herein find application are those where materialsrequiring a combination of stiffness and impact resistance and/or acombination of heat resistance and impact resistance. A plasticizedpolymer blend useful for these applications are similar in compositionto the blends specified for impact resistant devices and packages. Moreparticularly, plasticized polymer blends useful for this particularapplication may include from 51 to 99 wt % of a stiff propylenehomopolymer and/or a relatively stiff, low comonomer containingpropylene copolymer and 1-49 wt % of a plasticizer. The stiffness andheat resistance may be increased by increasing the homopolymer or stiffcopolymer portion of the polymer blend. Correspondingly, the impactresistance may be improved by increasing the plasticizer portion of theblend. The desired balance of product attributes may be accomplished bya careful balancing of the two components.

Still yet another exemplary, but non-limiting application of where theplasticized polymer blends made by the fluid phase in-line blendingprocess disclosed herein find application are those where a deviceand/or package must be sterilized by high temperature and also must besoft and able to withstand impact abuse even at low temperatures.Plasticized polymer blends useful for this particular application mayinclude from 75-99 wt % of one or more stiff homopolymer and/orcopolymer components and 1-25 wt % of one or more plasticizers. Whereincreasing softness of packages and device is desired, one may use agreater fraction of plasticizer in the blend, including to the pointthat the plasticizer is the majority component of the blend. Hence therange of polymer blends may include 10-95 wt % of the plasticizercomponent.

Still yet another exemplary, but non-limiting application of where theplasticized polymer blends made by the fluid phase in-line blendingprocess disclosed herein find application are films which are requiredto melt and form a seal at relatively low elevated temperature yet stillmaintain integrity at much higher temperature. The range of blendcompositions previously specified for soft, elevated temperatureresistant devices and/or packages would apply for this particular typeof film application. Similar relationships between competing propertiesand the relative usages of the relative components would also apply forthis application. More particularly, a greater fraction of the stiffpolymer component may increase the seal integrity at highertemperatures, whereas a greater fraction of the plasticizer componentmay improve seal formation at lower temperatures and seal strength atnormal temperatures.

As will be appreciated by one skilled in the art of polymer engineering,variations to the aforementioned plasticized polymer blends and theiradvantageous applications may be made without deviating from the spiritof the plasticized polymer blends provided by fluid phase in-lineblending process disclosed herein.

Catalyst System Overview:

The in-line process for blending polymers disclosed herein may utilizeany number of catalyst systems (also referred to as catalysts) in any ofthe reactors of the polymerization reactor section of the process. Thein-line process for blending polymers disclosed herein may also utilizethe same or different catalysts or catalyst mixtures in the differentindividual reactors of the reactor bank of the present invention. Itshould be understood that by using different catalyst systems we meanthat any part of the catalyst system can vary and any combination isallowed. For example, the invention process may use unsupported catalystsystems in some trains while using supported catalyst systems in othertrains. In other embodiments, the catalyst systems in some reactortrains may comprise aluminoxane (for example, MAO) activator, whilecomprising non-coordinating anion activators in some other trains. Inanother embodiments, the catalyst systems in some reactor trains maycomprise Ziegler-Natta catalysts, while the catalyst systems in otherreactor trains of the invention process may comprise metallocenes ornonmetallocene catalysts used for the production of Versify™ family ofpolymers activated by aluminoxane or non-coordinating anion activatorsor any combinations thereof. While the number of different catalystsystems deployed in the invention processes can be any number, the useof no more than five different catalysts and more particularly, no morethan three different catalysts in any given reactor is advantageous foreconomic reasons. The deployment of no more than ten catalysts or thedeployment of no more than six catalysts in the reactor bank of thepolymerization process is advantageous for economic reasons. The one ormore catalysts deployed in the reactors may be homogeneously dissolvedin the fluid reaction medium or may form a heterogeneous solid phase inthe reactor. In one particular embodiment, the catalyst(s) is (are)homogeneously dissolved in the fluid reaction medium. When the catalystis present as a solid phase in the polymerization reactor, it may besupported or unsupported.

The process disclosed herein may use any combination of homogeneous andheterogeneous catalyst systems simultaneously present in one or more ofthe individual reactors of the polymerization reactor section, i.e., anyreactor of the polymerization section of the present invention maycontain one or more homogeneous catalyst systems and one or moreheterogeneous catalyst systems simultaneously. The process disclosedherein may also use any combination of homogeneous and heterogeneouscatalyst systems deployed in the polymerization reactor section. Thesecombinations comprise scenarios when some or all reactors use a singlecatalyst and scenarios when some or all reactors use more than onecatalyst. The one or more catalysts deployed in the process disclosedherein may be supported on particles, which either can be dispersed inthe fluid polymerization medium or may be contained in a stationarycatalyst bed. When the supported catalyst particles are dispersed in thefluid reaction medium, they may be left in the polymeric product or maybe separated from the product prior to its crystallization from thefluid reactor effluent in a separation step that is downstream of thepolymerization reactor section. If the catalyst particles are recovered,they may be either discarded or may be recycled with or withoutregeneration.

The catalyst may also be supported on structured supports, such as forexample, monoliths comprising straight or tortuous channels, reactorwalls, internal tubing. When the catalysts are supported, operation maytake place on dispersed particles. When the catalyst is supported ondispersed particles, operations may take place without catalyst recoveryi.e., the catalyst is left in the polymeric product. In anotherembodiment, unsupported catalysts may be dissolved in the fluid reactionmedium.

Catalyst systems may be introduced into the reactor by any number ofmethods. For example, the catalyst may be introduced with themonomer-containing feed or separately. Also, the catalyst(s) may beintroduced through one or multiple ports to the reactor. If multipleports are used for introducing the catalyst, those ports may be placedat essentially the same or at different positions along the length ofthe reactor. If multiple ports are used for introducing the catalyst,the composition and the amount of catalyst feed through the individualports may be the same or different. Adjustment in the amounts and typesof catalyst through the different ports enables the modulation ofpolymer properties, such as for example, molecular weight distribution,composition, composition distribution, and crystallinity.

Catalyst Compounds and Mixtures:

The processes described herein may use any polymerization catalystcapable of polymerizing the monomers disclosed herein if that catalystis sufficiently active under the polymerization conditions disclosedherein. Thus, Group-3-10 transition metals may form suitablepolymerization catalysts. A suitable olefin polymerization catalyst willbe able to coordinate to, or otherwise associate with, an alkenylunsaturation. Illustrative, but not limiting, olefin polymerizationcatalysts include Ziegler-Natta catalyst compounds, metallocene catalystcompounds, late transition metal catalyst compounds, and othernon-metallocene catalyst compounds.

Distinction should made between active catalysts, also referred to ascatalyst systems herein, and catalyst precursor compounds. Catalystsystems are active catalysts comprising one or more catalyst precursorcompounds, one or more catalyst activators, and optionally, one or moresupports. Catalytic activity is often expressed based on theconcentration of the catalyst precursor compounds without implying thatthe active catalyst is the precursor compound alone. It should beunderstood that the catalyst precursor is inactive without beingcontacted or being treated with a proper amount of activator. Similarly,the catalyst activator is inactive without combining it with a properamount of precursor compound. As will become clear from the followingdescription, some activators are very efficient and can be usedstoichiometrically, while some others are used in excess, and insometimes large excess, to achieve high catalytic activity as expressedbased on the concentration of the catalyst precursor compounds. Sincesome of these activators, for example methylaluminoxane (MAO), increasecatalytic activity as expressed based on the concentration of thecatalyst precursor compounds, they are sometimes referred to as“cocatalysts” in the technical literature of polymerization.

As disclosed herein, Ziegler-Natta catalysts are those referred to asfirst, second, third, fourth, and fifth generation catalysts in thePROPYLENE HANDBOOK, E. P. Moore, Jr., Ed., Hanser, New York, 1996.Metallocene catalysts in the same reference are described as sixthgeneration catalysts. One exemplary non-metallocene catalyst compoundcomprises nonmetallocene metal-centered, heteroaryl ligand catalystcompounds (where the metal is chosen from the Group 4, 5, 6, thelanthanide series, or the actinide series of the Periodic Table of theElements).

Just as in the case of metallocene catalysts, these nonmetallocenemetal-centered, heteroaryl ligand catalyst compounds are typically madefresh by mixing a catalyst precursor compound with one or moreactivators. Nonmetallocene metal-centered, heteroaryl ligand catalystcompounds are described in detail in PCT Patent Publications Nos. WO02/38628, WO 03/040095 (pages 21 to 51), WO 03/040201 (pages 31 to 65),WO 03/040233 (pages 23 to 52), WO 03/040442 (pages 21 to 54), WO2006/38628, and U.S. patent application Ser. No. 11/714,546, each ofwhich is herein incorporated by reference.

Particularly useful metallocene catalyst and non-metallocene catalystcompounds are those disclosed in paragraphs [0081] to [0111] of U.S.Ser. No. 10/667,585 and paragraphs [0173] to [0293] of U.S. Ser. No.11/177,004, the paragraphs of which are herein incorporated byreference.

The processes disclosed herein can employ mixtures of catalyst compoundsto tailor the properties that are desired from the polymer. Mixedcatalyst systems prepared from more than one catalyst precursorcompounds can be employed in the in-line blending processes to alter orselect desired physical or molecular properties. For example, mixedcatalyst systems can control the molecular weight distribution ofisotactic polypropylene when used with the invention processes or forthe invention polymers. In one embodiment of the processes disclosedherein, the polymerization reaction(s) may be conducted with two or morecatalyst precursor compounds at the same time or in series. Inparticular, two different catalyst precursor compounds can be activatedwith the same or different activators and introduced into thepolymerization system at the same or different times. These systems canalso, optionally, be used with diene incorporation to facilitate longchain branching using mixed catalyst systems and high levels of vinylterminated polymers.

As disclosed herein, two or more of the above catalyst precursorcompounds can be used together.

Activators and Activation Methods for Catalyst Compounds:

The catalyst precursor compounds described herein are combined withactivators for use as active catalysts herein.

An activator is defined as any combination of reagents that increasesthe rate at which a metal complex polymerizes unsaturated monomers, suchas olefins. An activator may also affect the molecular weight, degree ofbranching, comonomer content, or other properties of the polymer.

A. Aluminoxane and Aluminum Alkyl Activators:

In one form, one or more aluminoxanes, such as methylaluminoxane, ortrialkylaluminum compounds, such as triisobutyl aluminum or tri-n-octylaluminum are utilized as an activator in the in-line blending processesdisclosed herein. Alkyl aluminoxanes, sometimes called alumoxanes in theart, are generally oligomeric compounds containing —Al(R)—O— subunits,where R is an alkyl group. Examples of aluminoxanes includemethylaluminoxane (MAO), modified methylaluminoxane (MMAO),ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modifiedalkylaluminoxanes are suitable as catalyst activators, particularly whenthe abstractable ligand is a halide. Mixtures of different aluminoxanesand modified aluminoxanes may also be used. For further descriptions,see U.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352,5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and European andPCT Patent Publication Nos. EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516476 A, EP 0 594 218 A1 and WO 94/10180, all of which are hereinincorporated by reference in their entirety.

When the activator is an aluminoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess, or at a 1000-fold molar excess, or at a 500-fold molar excessAl/Transition Metal over the catalyst compound (per metal catalyticsite). The minimum activator-to-catalyst-compound is typically a 1:1molar ratio.

B. Ionizing Activators:

It is contemplated to use an ionizing or stoichiometric activator,neutral or ionic, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron, a trisperfluorophenyl borone metalloidprecursor or a trisperfluoronaphtyl borone metalloid precursor,polyhalogenated heteroborane anions (PCT patent publication no. WO98/43983), boric acid (U.S. Pat. No. 5,942,459) or combination thereofas an activator herein. Also contemplated for use herein are neutral orionic activators alone or in combination with aluminoxane or modifiedaluminoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, aluminum, gallium and indium or mixtures thereof. The threesubstituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. The three groups are independently selected from halogen, monoor multicyclic (including halosubstituted) aryls, alkyls, and alkenylcompounds and mixtures thereof, advantageous are alkenyl groups having 1to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxygroups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbonatoms (including substituted aryls). Alternately, the three groups arealkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof.Alternately, the three groups are halogenated, or fluorinated, arylgroups. Alternately, the neutral stoichiometric activator istrisperfluorophenyl boron or trisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European patent publication Nos.EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference. Some of the useful activatorschosen from trimethylammonium tetraphenylborate, trisperfluorophenylborane, trisperfluoronaphtyl borane, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate,triethylammonium tetrakis(pentafluorophenyl)-borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, N,N-diethylaniliniumtetrakispentafluorophenyl) borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,tri(n-butyl)-ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate,dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, di-(1-propyl)ammonium tetrakis(pentafluorophenyl) borate,dicyclohexyl-ammonium tetrakis(pentafluorophenyl) borate,triphenylphosphonium tetrakis(pentafluorophenyl) borate,tri(o-tolyl)phosphonium tetrakis(pentafluoro-phenyl) borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate,N,N-dimethyl-anilinium tetra(perfluorophenyl)borate, triphenylcarbeniumtetra(perfluorophenyl)-borate, and combinations thereof. Some of theuseful activators are represented by the following formula:

(S^(t+))_(u)(NCA^(V−))_(w)

wherein:S^(t+) is a cation component having the charge t+NCA^(V−) is a non-coordinating anion having the charge v−t is an integer from 1 to 3;v is an integer from 1 to 3;u and v are constrained by the relationship: (u)×(t)=(v)×(w); whereS^(t+)) is a Bronsted acids or a reducible Lewis acids capable ofprotonating or abstracting a moiety.

C. Non-Ionizing Activators:

Activators are typically strong Lewis-acids which may play either therole of ionizing or non-ionizing activator. Activators previouslydescribed as ionizing activators may also be used as non-ionizingactivators.

Abstraction of formal neutral ligands may be achieved with Lewis acidsthat display an affinity for the formal neutral ligands. These Lewisacids are typically unsaturated or weakly coordinated. Examples ofnon-ionizing activators include R¹⁰(R¹¹)₃, where R¹⁰ is a group 13element and R¹¹ is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl,or a functional group. Typically, R¹¹ is an arene or a perfluorinatedarene. Non-ionizing activators also include weakly coordinatedtransition metal compounds such as low valent olefin complexes.

Non-limiting examples of non-ionizing activators include BMe₃, BEt₃,B(iBu)₃, BPh₃, B(C₆F₅)₃, AlMe₃, AlEt₃, Al(iBu)₃, AlPh₃, B(C₆F₅)₃,aluminoxane, CuCl, Ni(1,5-cyclooctadiene)₂.

Additional neutral Lewis-acids are known in the art and will be suitablefor abstracting formal neutral ligands. See in particular the reviewarticle by E. Y.-X. Chen and T. J. Marks, “Cocatalysts forMetal-Catalyzed Olefin Polymerization Activators, Activation Processes,and Structure-Activity Relationships”, Chem. Rev., 100, 1391-1434(2000).

Suitable non-ionizing activators include R¹⁰(R¹¹)₃, where R¹⁰ is a group13 element and R¹¹ is a hydrogen, a hydrocarbyl, a substitutedhydrocarbyl, or a functional group. Typically, R¹¹ is an arene or aperfluorinated arene.

Other non-ionizing activators include B(R¹²)₃, where R¹² is an arene ora perfluorinated arene. Alternately, non-ionizing activators includeB(C₆H₅)₃ and B(C₆F₅)₃. Another non-ionizing activator is B(C₆F₅)₃.Alternatively, activators include ionizing and non-ionizing activatorsbased on perfluoroaryl borane and perfluoroaryl borates such asPhNMe₂H⁺B(C₆F₅)₄ ⁻, (C₆H₅)₃C⁺B(C₆F₅)₄ ⁻, and B(C₆F₅)₃.

Additional activators that may be used with the catalyst compoundsdisclosed herein include those described in PCT patent publication No.WO 03/064433A1, which is incorporated by reference herein in itsentirety.

Additional useful activators for use in the processes disclosed hereininclude clays that have been treated with acids (such as H₂SO₄) and thencombined with metal alkyls (such as triethylaluminum) as described inU.S. Pat. No. 6,531,552 and EP Patent No. 1 160 261 A1, which areincorporated by reference herein.

Activators also may be supports and include ion-exchange layeredsilicate having an acid site of at most −8.2 pKa, the amount of the acidsite is equivalent to at least 0.05 mmol/g of 2,6-dimethylpyridineconsumed for neutralization. Non-limiting examples include chemicallytreated smectite group silicates, acid-treated smectite group silicates.Additional examples of the ion-exchange layered silicate include layeredsilicates having a 1:1 type structure or a 2:1 type structure asdescribed in “Clay Minerals (Nendo Kobutsu Gaku)” written by HaruoShiramizu (published by Asakura Shoten in 1995).

Examples of an ion-exchange layered silicate comprising the 1:1 layer asthe main constituting layer include kaolin group silicates such asdickite, nacrite, kaolinite, metahalloysite, halloysite or the like, andserpentine group silicates such as chrysotile, lizaldite, antigorite orthe like. Additional non-limiting examples of the ion-exchange layeredsilicate include ion-exchange layered silicates comprising the 2:2 layeras the main constituting layer include smectite group silicates such asmontmorillonite, beidellite, nontronite, saponite, hectorite,stephensite or the like, vermiculite group silicates such as vermiculiteor the like, mica group silicates such as mica, illite, sericite,glauconite or the like, and attapulgite, sepiolite, palygorskite,bentonite, pyrophyllite, talc, chlorites and the like. The clays arecontacted with an acid, a salt, an alkali, an oxidizing agent, areducing agent or a treating agent containing a compound intercalatablebetween layers of an ion-exchange layered silicate. The intercalationmeans to introduce other material between layers of a layered material,and the material to be introduced is called as a guest compound. Amongthese treatments, acid treatment or salt treatment is particularlyadvantageous. The treated clay may then be contacted with an activatorcompound, such as TEAL, and the catalyst compound to polymerize olefins.

In another form, the polymerization systems comprise less than 5 weight% polar species, or less than 4 weight %, or less than 3 weight %, orless than 2 weight %, or less than 1 weight %, or less than 1000 ppm, orless than 750 ppm, or less than 500 ppm, or less than 250 ppm, or lessthan 100 ppm, or less than 50 ppm, or less than 10 ppm. Polar speciesinclude oxygen containing compounds (except for alumoxanes) such asalcohols, oxygen, ketones, aldehydes, acids, esters and ethers.

In yet another form, the polymerization systems comprise less than 5weight % trimethylaluminum and/or triethylaluminum, or less than 4weight %, or less than 3 weight %, or less than 2 weight %, or less than1 weight %, or less than 1000 ppm, or less than 750 ppm, or less than500 ppm, or less than 250 ppm, or less than 100 ppm, or less than 50ppm, or less than 10 ppm.

In still yet another form, the polymerization systems comprisemethylaluminoxane and less than 5 weight % trimethylaluminum and ortriethylaluminum, or less than 4 weight %, or less than 3 weight %, orless than 2 weight %, or less than 1 weight %, or less than 1000 ppm, orless than 750 ppm, or less than 500 ppm, or less than 250 ppm, or lessthan 100 ppm, or less than 50 ppm, or less than 10 ppm.

The in-line blending processes disclosed herein may use finely divided,supported catalysts to prepare propylene/1-hexene copolymers withgreater than 1.0 mole % 1-hexene. In addition to finely dividedsupports, in-line blending processes disclosed herein may use fumedsilica supports in which the support particle diameter may range from200 angstroms to 1500 angstroms, small enough to form a colloid withreaction media.

Catalyst Supports:

In another form, the catalyst compositions of fluid phase in-lineblending processes disclosed herein may include a support material orcarrier. For example, the one or more catalyst components and/or one ormore activators may be deposited on, contacted with, vaporized with,bonded to, or incorporated within, adsorbed or absorbed in, or on, oneor more supports or carriers.

The support material may be any of the conventional support materials.In one form, the supported material may be a porous support material,for example, talcs, inorganic oxides, and inorganic chlorides,polystyrene, polystyrene divinyl benzene polyolefins, zeolites, clays,silica, fumed silica, alumina, silica-alumina, magnesia, titania,zirconia, magnesium chloride, montmorillonite phyllosilicate, porousacrylic polymers, nanocomposites, spherulites, polymeric beads andcombinations thereof. Other support materials may include resinoussupport materials such as polystyrene, functionalized or crosslinkedorganic supports, such as polystyrene divinyl benzene polyolefins orpolymeric compounds, zeolites, clays, or any other organic or inorganicsupport material and the like, or mixtures thereof.

Useful support materials are inorganic oxides that include those Group2, 3, 4, 5, 13 or 14 metal oxides. In one form, the supports includesilica, which may or may not be dehydrated, fumed silica, alumina (PCTpatent publication No. WO 99/60033), silica-alumina and mixturesthereof. Other useful supports include magnesia, titania, zirconia,magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EuropeanPatent No. EP-B 10 511 665), phyllosilicate, zeolites, talc, clays (U.S.Pat. No. 6,034,187) and the like. Also, combinations of these supportmaterials may be used, for example, silica-chromium, silica-alumina,silica-titania and the like. Additional support materials may includethose porous acrylic polymers described in European Patent No. EP 0 767184 B1, which is incorporated herein by reference. Other supportmaterials include nanocomposites as described in PCT WO 99/47598,aerogels as described in WO 99/48605, spherulites as described in U.S.Pat. No. 5,972,510 and polymeric beads as described in WO 99/50311,which are all herein incorporated by reference.

The support material, for example an inorganic oxide, has a surface areain the range of from about 10 to about 700 m²/g, pore volume in therange of from about 0 to about 4.0 cc/g and average particle size in therange of from about 0.02 to about 50 μm. Alternatively, the surface areaof the support material is in the range of from about 50 to about 500m²/g, pore volume of from about 0 to about 3.5 cc/g and average particlesize of from about 0.02 to about 20 μm. In another form, the surfacearea of the support material is in the range is from about 100 to about400 m²/g, pore volume from about 0 to about 3.0 cc/g and averageparticle size is from about 0.02 to about 10 μm.

Non-porous supports may also be used as supports in the processesdescribed herein. For example, in a one embodiment the nonporous, fumedsilica supports described in U.S. Pat. No. 6,590,055 may be used and isincorporated by reference herein.

Scavengers:

Compounds that destroy impurities are referred to as scavengers by oneskilled in the art of polymerization. Impurities may harm catalysts byreducing their activity. Scavengers may be optionally fed to thereactor(s) of the in-line blending process disclosed herein. Catalyticactivity may be defined many different ways. For example, catalyticactivity can be expressed as turnover frequency, i.e., the number ofmoles of monomers converted to the product in a unit time by one mole ofcatalyst precursor employed in preparing the active catalyst system. Fora given reactor operating at the same residence time, catalytic activitymay also be measured in terms of catalyst productivity, customarilyexpressed as the weight of polymer made by a unit weight of catalystprecursor with or without the weight of the activator.

The scavengers for use in the processes disclosed herein may bedifferent chemical compound(s) from the catalyst activator. Non-limitingexemplary scavengers include diethyl zinc, and alkyl aluminum compounds,such as trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum,and trioctyl aluminum. The scavenger may also be the same as thecatalyst activator and is generally applied in excess of what is neededto fully activate the catalyst. These scavengers include, but are notlimited to, aluminoxanes, such as methyl aluminoxane. The scavenger mayalso be introduced to the reactor with the monomer feed or with anyother feed stream. In one particular embodiment, the scavenger isintroduced with the monomer-containing feed. The scavenger may behomogeneously dissolved in the polymerization reaction medium or mayform a separate solid phase. In one particular embodiment, scavengersare dissolved in the polymerization medium.

Reaction Monomers and Comonomers:

The processes disclosed herein may be used to polymerize any monomerhaving one or more (non-conjugated) aliphatic double bond(s) and two ormore carbon atoms. In the embodiments producing one or more plasticizersin-line, the monomers used for making the base polymer and for makingthe plasticizer components of the in-line-plasticized polymers, polymerblends, and polymer masterbatches are often of the same type, forexample, the base polymer may be made of propylene (an aliphatic olefin)and the plasticizer may be made of ethylene and propylene or higheralpha-olefins. The most commonly used monomers for making the basepolymer components are ethylene and propylene and their combinationswith each other or (to a smaller degree) with lower concentrations ofmonomers that modify the parent polymer by, for example, introducinglong-chain branching as done with alpha-omega dienes. These combinationsare well known in the art of olefin polymerization. Useful monomers forproducing and blending plasticizers in-line include mixed C₆-C₁₄ linear1-olefins, ethylene-butene, ethylene-hexene, ethylene-octene, propylene,propylene-butene, propylene-hexene mixtures, styrene and alpha-methylstyrene. Monomers for use in the in-line blending process thus includeethylene, propylene, C₄ and higher α-olefins (non-limiting examplesinclude butene-1, hexene-1, octene-1, and decene-1); substituted olefins(non-limiting examples include styrene, and vinylcyclohexane);non-conjugated dienes (non-limiting examples include vinylcyclohexene,dicyclopentadiene); α,ω-dienes (non-limiting examples include1,5-hexadiene, 1,7-octadiene); cycloolefins (non-limiting examplesinclude cyclopentene, cyclohexene); and norbornene.

The processes disclosed herein may be used to polymerize any unsaturatedmonomer or monomers including C₃ to C₁₀₀ olefins, alternatively C₃ toC₆₀ olefins, alternatively C₃ to C₄₀ olefins, alternatively C₃ to C₂₀olefins, and alternately C₃ to C₁₂ olefins. The processes disclosedherein may also be used to polymerize linear, branched or cyclicalpha-olefins including C₃ to C₁₀₀ alpha-olefins, alternatively C₃ toC₆₀ alpha-olefins, alternately C₃ to C₄₀ alpha-olefins, alternatively C₅to C₂₀ alpha-olefins, and alternatively C₅ to C₁₂ alpha-olefins.Suitable olefin monomers may be one or more of propylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methyl-pentene-1,3-methyl pentene-1,3,5,5-trimethyl-hexene-1, and5-ethylnonene-1. C₅ to C₂₀ alpha-olefins and their mixtures areparticularly useful for making plasticizer poly(alpha-olefins) alsoreferred to as PAOs. The mixtures of ethylene and propylene areparticularly useful for making ethylene-propylene plasticizer copolymerssuch as plastomers, elastomers, and other ethylene-propylene plasticizercopolymers.

In another embodiment of the processes disclosed herein, the polymerproduced herein is a copolymer of one or more linear or branched C₃ toC₃₀ prochiral alpha-olefins or C₅ to C₃₀ ring containing olefins orcombinations thereof capable of being polymerized by eitherstereospecific and non-stereospecific catalysts. Prochiral, as usedherein, refers to monomers that favor the formation of isotactic orsyndiotactic polymer when polymerized using stereospecific catalyst(s).

Other monomers for use with the in-line blending process disclosedherein may also include aromatic-group-containing monomers containing upto 30 carbon atoms. Suitable aromatic-group-containing monomers compriseat least one aromatic structure, alternately from one to three, andalternately a phenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure is pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C₁ to C₁₀ alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Aromatic-group-containing monomers may also contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Non-limiting exemplary aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, and alternatively styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers may also be used in theprocesses disclosed herein. These monomers may include up to 30 carbonatoms. Suitable non-aromatic cyclic group containing monomers may haveat least one polymerizable olefinic group that is either pendant on thecyclic structure or is part of the cyclic structure. The cyclicstructure may also be further substituted by one or more hydrocarbylgroups, for example, but not limited to, C₁ to C₁₀ alkyl groups.Non-limiting exemplary non-aromatic cyclic group containing monomersinclude vinylcyclohexane, vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, andvinyladamantane.

Diolefin monomers may also be used in the processes disclosed herein.These diolefin monomers include any hydrocarbon structure, oralternatively C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).The diolefin monomers may also be selected from alpha, omega-dienemonomers (i.e. di-vinyl monomers), alternatively linear di-vinylmonomers containing from 4 to 30 carbon atoms. Non-limiting exemplarydienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene,nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene,tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene,particularly advantageous dienes include 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weightpolybutadienes (Mw less than 1000 g/mol). Non-limiting exemplary cyclicdienes include cyclopentadiene, vinylnorbornene, norbornadiene,ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ringcontaining diolefins with or without substituents at various ringpositions.

Non-limiting examples of polar unsaturated monomers include6-nitro-1-hexene, N-methylallylamine, N-allylcyclopentylamine,N-allyl-hexylamine, methyl vinyl ketone, ethyl vinyl ketone,5-hexen-2-one, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, acrolein, 2,2-dimethyl-4-pentenal,undecylenic aldehyde, 2,4-dimethyl-2,6-heptadienal, acrylic acid,vinylacetic acid, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid,6-heptenoic acid, trans-2,4-pentadienoic acid, 2,6-heptadienoic acid,nona-fluoro-1-hexene, allyl alcohol, 7-octene-1,2-diol,2-methyl-3-buten-1-ol, 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, allyl 1,1,2,2,-tetrafluoroethyl ether, acroleindimethyl acetal, butadiene monoxide, 1,2-epoxy-7-octene,1,2-epoxy-9-decene, 1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allylglycidyl ether, 2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal,allyl disulfide, ethyl acrylate, methyl acrylate.

Polymerizations may be carried out with any suitable feed composition toyield the desired product composition at an economical single-passconversion. Monomer concentrations are generally lower when substantialamounts of inert solvents/diluents are cofed with the monomers andcatalyst. Although inert solvents/diluents may be used if so desired,low solvent/diluent concentration is often advantageous due to reducedsolvent and monomer recovery-recycle cost. In one embodiment, olefinpolymerization is carried out in the presence of less than 60 wt % ofinert solvent/diluent affording olefin concentrations in the combinedfeeds of the individual reators of 40 wt % or more, or even 55 wt % ormore, and advantageously 75 wt % or more.

In another embodiment, polymerizations yielding the in-line blendcomponents are carried out in bulk monomer phases, i.e., with combinedreactor feeds comprising inert solvent/diluent at less than 40 wt %, orless than 30 wt %, or less than 20 wt %, or less than 15 wt %, or lessthan 10 wt %, or less than 5 wt %, or even less than 1 wt %.

In a particular embodiment, ethylene-propylene copolymer blendcomponents are made with essentially diluent-free monomer feedscontaining 1-18 wt % ethylene and 75-99 wt % propylene. In anotherembodiment, ethylene-propylene copolymer blend components are producedwith essentially diluent-free monomer feeds containing 5-30 wt % ofbutene-1, or hexene-1 and 65-95 wt % of propylene or ethylene.

The processes disclosed herein may be used to produce homopolymers orcopolymers. A copolymer refers to a polymer synthesized from two, three,or more different monomer units. Polymers produced by the processesdisclosed herein include homopolymers or copolymers of any of the abovemonomers.

In one embodiment of the processes disclosed herein, the polymer is ahomopolymer of any C₃ to C₁₂ alpha-olefin, or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingpropylene and ethylene wherein the copolymer comprises less than 70weight % ethylene, or less than 60 weight % ethylene, or less than 40weight % ethylene, or less than 20 weight % ethylene. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another embodiment, thecopolymers comprise one or more diolefin comonomers, alternatively oneor more C₆ to C₄₀ non-conjugated diolefins, alternatively one or more C₆to C₄₀ α,ω-dienes.

In another embodiment of the processes disclosed herein, the one or morepolymer blend components are a copolymer of ethylene, propylene, orother higher olefin and optionally any third monomer, typically anotherhigher olefin, such as C₄ to C₂₀ linear, branched or cyclic monomers. Inanother embodiment, the one or more polymer blend components producedherein are a copolymer of ethylene and one or more of propylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methyl-pentene-1,3-methyl pentene-1, and 3,5,5-trimethyl-hexene-1. Instill another embodiment, the one or more polymer blend componentsproduced herein are a copolymer of propylene and one or more ofethylene, butene, pentene, hexene, heptene, octene, nonene, decene,dodecene, 4-methyl-pentene-1,3-methyl-pentene-1, and3,5,5-trimethyl-hexene-1. In still yet another embodiment, the one ormore polymer blend components produced herein are a copolymer of a C₄ orhigher olefin and one or more of ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene,4-methyl-pentene-1,3-methyl-pentene-1, and 3,5,5-trimethyl-hexene-1.

In another embodiment of the processes disclosed herein, the copolymersdescribed comprise at least 50 mole % of a first monomer and up to 50mole % of other monomers. In another embodiment, the polymer comprises:a first monomer present at from 40 to 95 mole %, or 50 to 90 mole %, or60 to 80 mole %, and a comonomer present at from 5 to 40 mole %, or 10to 60 mole %, or 20 to 40 mole %, and a termonomer present at from 0 to10 mole %, or from 0.5 to 5 mole %, or from 1 to 3 mole %. Suchcopolymer blending components can be readily produced when thecomonomer(s) is (are) present between 0.1 and 85 mole % in the combinedfeeds to the reactor making the copolymers.

In another embodiment of the processes disclosed herein, the firstmonomer comprises one or more of any C₃ to C₈ linear branched or cyclicalpha-olefins, including propylene, butene, (and all isomers thereof),pentene (and all isomers thereof), hexene (and all isomers thereof),heptene (and all isomers thereof), and octene (and all isomers thereof).Advantageous monomers include propylene, 1-butene, 1-hexene, 1-octene,cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like.

In another embodiment of the processes disclosed herein, the comonomercomprises one or more of any C₂ to C₄₀ linear, branched or cyclicalpha-olefins (provided ethylene, if present, is present at 5 mole % orless), including ethylene, propylene, butene, pentene, hexene, heptene,and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene,hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene,dodecadiene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

In another embodiment of the processes disclosed herein, the termonomercomprises one or more of any C₂ to C₄₀ linear, branched or cyclicalpha-olefins, (provided ethylene, if present, is present at 5 mole % orless), including ethylene, propylene, butene, pentene, hexene, heptene,and octene, nonene, decene, un-decene, dodecene, hexadecene, butadiene,hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene,dodecadiene, styrene,3,5,5-trimethyl-hexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

In another embodiment of the processes disclosed herein, the polymersdescribed above further comprise one or more dienes at up to 10 weight%, or at 0.00001 to 1.0 weight %, or at 0.002 to 0.5 weight %, or at0.003 to 0.2 weight %, based upon the total weight of the composition.In some embodiments 500 ppm or less of diene is added to the combinedfeed of one or more polymerization trains, alternately 400 ppm or less,alternatively 300 ppm or less. In other embodiments at least 50 ppm ofdiene is added to the combined feed of one or more polymerizationtrains, or 100 ppm or more, or 150 ppm or more. In yet anotherembodiment the concentration of diene in the combined feed to thereactor is between 50 wt ppm and 10,000 wt ppm.

In another embodiment of the processes disclosed herein, the processesused to produce propylene copolymers with other monomer units, such asethylene, other α-olefin, α-olefinic diolefin, or non-conjugateddiolefin monomers, for example C₄-C₂₀ olefins, C₄-C₂₀ diolefins, C₄-C₂₀cyclic olefins, C₈-C₂₀ styrenic olefins. Other unsaturated monomersbesides those specifically described above may be copolymerized usingthe processes disclosed herein, for example, styrene, alkyl-substitutedstyrene, ethylidene norbornene, norbornadiene, dicyclopentadiene,vinylcyclohexane, vinylcyclohexene, acrylates, and otherolefinically-unsaturated monomers, including other cyclic olefins, suchas cyclopentene, norbornene, and alkyl-substituted norbornenes.Copolymerization can also incorporate α-olefinic macromonomers producedin-situ or added from another source. Some embodiments limit thecopolymerization of α-olefinic macromonomers to macromonomers with 2000or less mer units. U.S. Pat. No. 6,300,451 discloses many usefulcomonomers. That disclosure refers to comonomers as “a second monomer.”

In another embodiment of the processes disclosed herein, when propylenecopolymers are desired, the following monomers can be copolymerized withpropylene: ethylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene,dicyclopentadiene, norbornene, C₄-C₂₀₀₀, C₄-C₂₀₀, or C₄-C₄₀ linear orbranched, α,ω-dienes; C₄-C₂₀₀₀, C₄-C₂₀₀, or C₄-C₄₀ cyclic olefins; andC₄-C₂₀₀₀, C₄-C₂₀₀, or C₄-C₄₀ linear or branched α-olefins.

Other Primary Monomer:

The polymerization processes disclosed herein may polymerize butene-1(T_(c)=146.5° C.; P_(c)=3.56 MPa), pentene-1 (T_(c)=191.8° C.;P_(c)=3.56 MPa), hexene-1 (T_(c)=230.8° C.; P_(c)=3.21 MPa),3-methyl-butene-1 (T_(c)=179.7° C.; P_(c)=3.53 MPa), and4-methyl-pentene-1 using these monomers or mixtures comprising themonomers at supercritical conditions or as a liquid. These processes mayemploy at least one of butene-1, pentene-1, or 3-methyl-butene-1 asmonomer. These processes may also employ reaction media that comprisebutene-1, pentene-1,3-methyl-butene-1 or 4-methyl-pentene-1. Theseprocesses can employ polymerization feeds that contain greater than 50mole % of butene-1, pentene-1, or 3-methyl-butene-1 and theirconcentration can vary between 0.1 and 85 mole %. Of course, thesecompounds can be freely mixed with each other and with propylene asmonomer, bulk reaction media, or both.

Reaction Solvents/Diluents:

Solvent and or diluent may be present in the polymerization system. Anyhydrocarbon, fluorocarbon, or fluorohydrocarbon inert solvent or theirmixtures may be used at concentrations not more than 80 wt % in thefeeds to any individual polymerization reactor of the in-line blendingprocess disclosed herein. The concentration of the inert solvent in thereactor feed and thus in the polymerization system in certainembodiments utilizing bulk polymerization processes is not more than 40wt %, or not more than 30 wt %, or not more than 20 wt %, alternativelynot more than 10 wt %, alternatively not more than 5 wt %, andalternatively not more than 1 wt %.

Diluents for use in the in-line blending process disclosed herein mayinclude one or more of C₂-C₂₄ alkanes, such as ethane, propane,n-butane, i-butane, n-pentane, i-pentane, n-hexane, mixed hexanes,cyclopentane, cyclohexane, etc., single-ring aromatics, such as tolueneand xylenes. In some embodiments, the diluent comprises one or more ofethane, propane, butane, isobutane, pentane, isopentane, and hexanes. Inother embodiments, the diluent is recyclable.

Other diluents may also include C₄ to C₁₅₀ isoparaffins, or C₄ to C₁₀₀isoparaffins, or C₄ to C₂₅ isoparaffins, or C₄ to C₂₀ isoparaffins. Byisoparaffin is meant that the paraffin chains possess C₁ to C₁₀ alkylbranching along at least a portion of each paraffin chain. Moreparticularly, the isoparaffins are saturated aliphatic hydrocarbonswhose molecules have at least one carbon atom bonded to at least threeother carbon atoms or at least one side chain (i.e., a molecule havingone or more tertiary or quaternary carbon atoms), and advantageouslywherein the total number of carbon atoms per molecule is in the rangebetween 6 to 50, and between 10 and 24 in another embodiment, and from10 to 15 in yet another embodiment. Various isomers of each carbonnumber will typically be present. The isoparaffins may also includecycloparaffins with branched side chains, generally as a minor componentof the isoparaffin. The density of these isoparaffins may range from0.70 to 0.83 g/cm³; the pour point is −40° C. or less, alternately −50°C. or less, the kinematic viscosity at 25° C. is from 0.5 to 20 cSt; andnumber-averaged molecular weight (Mn) in the range of 100 to 300 g/mol.Some suitable isoparaffins are commercially available under thetradename is ISOPAR (ExxonMobil Chemical Company, Houston Tex.), and aredescribed in, for example in U.S. Pat. Nos. 6,197,285, 3,818,105 and3,439,088, and sold commercially as ISOPAR series of isoparaffins. Othersuitable isoparaffins are also commercial available under the tradenames SHELLSOL, SOLTROL and SASOL. SHELLSOL is a product of the RoyalDutch/Shell Group of Companies, for example Shellsol™ (boilingpoint=215-260° C.). SOLTROL is a product of Chevron Phillips ChemicalCo. LP, for example SOLTROL 220 (boiling point=233-280° C.). SASOL is aproduct of Sasol Limited (Johannesburg, South Africa), for example SASOLLPA-210, SASOL-47 (boiling point=238-274° C.).

In another embodiment of the in-line blending process disclosed herein,diluents may include C₄ to C₂₅ n-paraffins, or C₄ to C₂₀ n-paraffins, orC₄ to C₁₅ n-paraffins having less than 0.1%, or less than 0.01%aromatics. Some suitable n-paraffins are commercially available underthe tradename NORPAR (ExxonMobil Chemical Company, Houston Tex.), andare sold commercially as NORPAR series of n-paraffins. In anotherembodiment, diluents may include dearomaticized aliphatic hydrocarboncomprising a mixture of normal paraffins, isoparaffins andcycloparaffins. Typically they are a mixture of C₄ to C₂₅ normalparaffins, isoparaffins and cycloparaffins, or C₅ to C₁₈, or C₅ to C₁₂.hey contain very low levels of aromatic hydrocarbons, or less than 0.1,or less than 0.01 aromatics. Suitable dearomatized aliphatichydrocarbons are commercially available under the tradename EXXSOL(ExxonMobil Chemical Company, Houston Tex.), and are sold commerciallyas EXXSOL series of dearomaticized aliphatic hydrocarbons.

In another embodiment of the in-line blending process disclosed herein,the inert diluent comprises up to 20 weight % of oligomers of C₆ to C₁₄olefins and/or oligomers of linear olefins having 6 to 14 carbon atoms,or 8 to 12 carbon atoms, or 10 carbon atoms having a Kinematic viscosityat 100° C. of 2 cSt or more, or 4 cSt or more, or 6 cSt or more, or 8cSt or more, or 10 cSt or more.

In another embodiment of the fluid phase in-line process for blendingdisclosed herein, the inert diluent comprises up to 20 weight % ofoligomers of C₂₀ to C₁₅₀₀ paraffins, alternately C₄₀ to C₁₀₀₀ paraffins,alternately C₅₀ to C₇₅₀ paraffins, alternately C₅₀ to C₅₀₀ paraffins. Inanother embodiment of the fluid phase in-line process for blendingdisclosed herein, the diluent comprises up to 20 weight % of oligomersof 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene and 1-dodecene. Such oligomers are commercially availableSpectraSyn (ExxonMobil Chemical Company, Houston Tex.). Other usefuloligomers include those sold under the tradenames Synfluid™ availablefrom ChevronPhillips Chemical Co. in Pasedena Tex., Durasyn™ availablefrom Ineos in London England, Nexbase™ available from Fortum Oil and Gasin Finland, Synton™ available from Chemtura Corporation in MiddleburyConn., USA, EMERY™ available from Chemtura in Ohio, USA.

In another embodiment of the fluid phase in-line process for blendingdisclosed herein, the diluent comprises a flourinated hydrocarbon.Exemplary fluorocarbons include perfluorocarbons (“PFC” or “PFC's”) andor hydrofluorocarbons (“HFC” or “HFC's”), collectively referred to as“fluorinated hydrocarbons” or “fluorocarbons” (“FC” or “FC's”).Fluorocarbons are defined to be compounds consisting essentially of atleast one carbon atom and at least one fluorine atom, and optionallyhydrogen atom(s). A perfluorocarbon is a compound consisting essentiallyof carbon atom and fluorine atom, and includes for example linearbranched or cyclic, C₁ to C₄₀ perfluoroalkanes. A hydrofluorocarbon is acompound consisting essentially of carbon, fluorine and hydrogen. FC'sinclude those represented by the formula: C_(x)H_(y)F_(z) wherein x isan integer from 1 to 40, alternatively from 1 to 30, alternatively from1 to 20, alternatively from 1 to 10, alternatively from 1 to 6,alternatively from 2 to 20 alternatively from 3 to 10, alternativelyfrom 3 to 6, alternatively from 1 to 3, wherein y is an integer greaterthan or equal to 0 and z is an integer and at least one, alternatively,y and z are integers and at least one. For purposes of the in-lineblending processes disclosed herein and the claims thereto, the termshydrofluorocarbon and fluorocarbon do not include chlorofluorocarbons.

In one embodiment of the fluid phase in-line process for blendingdisclosed herein, a mixture of fluorocarbons are used, alternatively amixture of a perfluorinated hydrocarbon and a hydrofluorocarbon, andalternatively a mixture of a hydrofluorocarbons. In yet anotherembodiment, the hydrofluorocarbon is balanced or unbalanced in thenumber of fluorine atoms in the HFC used.

With regard to the polymerization media, suitable diluents and solventsare those that are soluble in and inert to the monomer and any otherpolymerization components at the polymerization temperatures andpressures.

Reactor Configuration:

The polymer and plasticizer reaction processes of the fluid phasein-line process for blending disclosed herein may be carried out in twoor more reactors making the polymers and plasticizers for downstreamblending. The reactors may be fed with essentially the same or differentfeeds and can run at essentially the same or different reactorconditions. The reactors may also produce essentially the same ordifferent polymeric products.

When multiple reactors are used in the processes disclosed herein, theproduction of plasticized polymer blends including two or more polymersis possible. In one embodiment, homopolymer and copolymer blends aremade by using at least two reactor trains in a parallel configuration.Non-limiting exemplary homopolymers include polyethylene, polypropylene,polybutene, polyhexene, and polyoctane. In one embodiment, thehomopolymer comprises polyethylene, polypropylene, polybutylene,polyhexene, and polystyrene. In another embodiment, the homopolymer ispolyethylene or polypropylene. The copolymers may be any two- orthree-component combinations of ethylene, propylene, butene-1, hexene-1,octene-1, styrene, norbornene, 1,5-hexadiene, and 1,7-octadiene. In oneembodiment, the copolymers are made from a two-component combination ofethylene, propylene, butene-1, hexene-1, styrene, norbornene,1,5-hexadiene, and 1,7-octadiene. In another embodiment, the copolymeris an ethylene-propylene, propylene-butene-1, propylene-hexene-1,propylene-octene-1, ethylene-butene-1, ethylene-hexene-1, and/orethylene-octene-1 copolymer.

As previously described, the in-line blending polymer components areproduced in a reactor bank composed of at least two parallel reactortrains. A reactor train of the parallel reactor bank may include one ormore reactors that may be configured in series configuration. The numberof parallel reactors trains or branches in a parallel bank may be anynumber, but for practical reasons, is generally limited to less thanten, alternatively not more than six parallel reactor trains,alternatively not more than five or not more than four reactor trains,alternatively not more than three parallel reactor trains, andalternatively not more than two parallel reactor trains. The number ofseries cascade reactors constituting a given reactor train or branch ofa parallel configuration may be any number, but for practical reasons,is generally limited to not more than ten reactors in series,alternatively not more than six reactors in series, alternatively notmore than three reactors in series, and alternatively not more than tworeactors in series.

In one embodiment, the base polymer containing effluent andplasticizer-containing effluent from two or more reactor trainsconfigured in a parallel configuration are combined yielding aplasticized polymer blend comprising the base polymer and plasticizerproducts of the individual reactors without first recovering the basepolymer and plasticizer products of the individual reactors in solid orliquid forms. The two or more reactor trains constituting the parallelconfiguration generally include a single reactor, or alternatively, twoor more reactors in series.

Another embodiment of the processes disclosed herein, blends the basepolymer containing effluent with one or more in-line-producedplasticizer and optionally one or more off-line-produced plasticizersin-line. The base polymer is blended in the form of a diluted effluentstream that contains at least some of the light components of thereactor effluent, such as the monomers and optional inertsolvent/diluents. Such streams are advantageous for in-line blending dueto their lower viscosity and thus enhanced ability for fluid phaseblending. However, unlike in the previously described embodiment, thein-line-produced plasticizer is blended as a fully recovered plasticizerfluid, i.e, in its essentially pure form. The full recovery of thein-line-produced plasticizer may be advantageous when the plasticizer isa liquid at ambient temperature, and/or when some of thein-line-produced plasticizer product is exported from the in-lineblending process for sales or for other uses. The base polymer andin-line-produced plasticizer components are produced in two or moreparallel reactor trains. The reactor trains constituting the parallelconfiguration generally include a single reactor, or alternatively, twoor more reactors in series.

The reactors of the polymerization system for the fluid phase in-lineprocess for blending disclosed herein may be stirred or unstirred. Whena reactor train comprises two or more reactors, the members of thereactor train are not necessarily constructed the same way, for example,the individual members of a reactor train may be stirred, unstirred, ora combination thereof. The individual reactors may also be of equal ordifferent size. The same is true for the reactors in the entire reactorbank. The optimal reactor configuration and sizes may be determined bystandard engineering techniques known to those skilled in the art ofchemical engineering.

Any type of reactor may be deployed in the fluid phase in-line processfor blending disclosed herein. The optimal reactor design may bedetermined by standard engineering techniques known to those skilled inthe art of chemical engineering. Non-limiting exemplary reactor designsinclude stirred tank with or without an external loop, tubular reactor,and loop reactor. The reactors may operate adiabatically or may becooled. The cooling may be achieved within the reactor, or through thereactor jacket, or dedicated heat exchange loops may be applied.

Reaction Process Details:

The fluid phase in-line process for blending disclosed herein relates toprocesses to polymerize or oligomerize olefins comprising contacting oneor more olefins having at least two carbon atoms with a suitablecatalyst compound and an activator in a fluid reaction medium comprisingone or two fluid phases in a reactor. Polymerization in a single fluidphase may be advantageous due to improved heat transfer and reducedtendency for fouling. In one embodiment, the fluid reaction medium is inits supercritical state. Catalyst compound and activator may bedelivered as a solution or slurry, either separately to the reactor,mixed in-line just prior to the reactor, or mixed and pumped as anactivated solution or slurry to the reactor. In one particularembodiment, two solutions are mixed in-line. For a given reactor trainof the parallel configuration, polymerizations may be carried out ineither single reactor operation, in which monomer, comonomers,catalyst(s)/activator(s), scavenger(s), and optional solvent(s) areadded continuously to a single reactor or in series reactor operation,in which the above components are added to two or more reactorsconnected in series. The catalyst components may be added to the firstreactor in the series. The catalyst component may also be added to eachreactor in the series reactor train. The fresh catalyst feed if added tomore than one reactor in the series train may be the same or differentto each reactor and their feed rates may be the same or different.

Some embodiments of the polymerization processes of the fluid phasein-line process for blending disclosed herein also comprehendhigh-pressure reactors where the reactor is substantially unreactivewith the polymerization reaction components and is able to withstand thehigh pressures and temperatures that occur during the polymerizationreaction. Withstanding these high pressures and temperatures may allowthe reactor to maintain the fluid reaction medium in its supercriticalcondition. Suitable reaction vessel designs include those necessary tomaintain supercritical or other high-pressure ethylene polymerizationreactions. Non-limiting exemplary reactors include autoclave,pump-around loop or autoclave, tubular, and autoclave/tubular reactors.

The polymerization processes of the fluid phase in-line process forblending disclosed herein may operate efficiently in autoclave (alsoreferred to as stirred tank) and tubular reactors. Autoclave reactorsmay be operated in either a batch or continuous mode, although thecontinuous mode is advantageous. Tubular reactors always operate incontinuous mode. Typically, autoclave reactors have length-to-diameterratios of 1:1 to 20:1 and are fitted with a high-speed (up to 2000 RPM)multiblade stirrer and baffles arranged for optimal mixing. Commercialautoclave pressures are typically greater than 5 MPa with a maximum oftypically less than 260 MPa. The maximum pressure of commercialautoclaves, however, may become higher with advances in mechanical andmaterial science technologies.

When the autoclave has a low length-to-diameter ratio (such as less thanfour), the feed streams may be injected at one position along the lengthof the reactor. Reactors with large diameters may have multipleinjection ports at nearly the same or different positions along thelength of the reactor. When they are positioned at the same length ofthe reactor, the injection ports are radially distributed to allow forfaster intermixing of the feed components with the reactor content. Inthe case of stirred tank reactors, the separate introduction of thecatalyst and monomer(s) may be advantageous in preventing the possibleformation of hot spots in the unstirred feed zone between the mixingpoint and the stirred zone of the reactor. Injections at two or morepositions along the length of the reactor is also possible and may beadvantageous. In one exemplary embodiment, in reactors where thelength-to-diameter ratio is from 4 to 20, the reactor may contain up tosix different injection positions along the reactor length with multipleports at some or each of the lengths.

Additionally, in the larger autoclaves, one or more lateral mixingdevices may support the high-speed stirrer. These mixing devices canalso divide the autoclave into two or more zones. Mixing blades on thestirrer may differ from zone to zone to allow for a different degree ofplug flow and back mixing, largely independently, in the separate zones.Two or more autoclaves with one or more zones may connect in a seriesreactor cascade to increase residence time or to tailor polymerstructure in a reactor train producing a polymer blending component. Aspreviously described, a series reactor cascade or configuration consistsof two or more reactors connected in series, in which the effluent of atleast one upstream reactor is fed to the next reactor downstream in thecascade. Besides the effluent of the upstream reactor(s), the feed ofany reactor in the series reactor cascade of a reactor train can beaugmented with any combination of additional monomer, catalyst, orsolvent fresh or recycled feed streams. Therefore, it should beunderstood that the polymer blending component leaving a reactor trainof the process disclosed herein may itself be a blend of the samepolymer with increased molecular weight and/or compositional dispersionor even a blend of homo- and copolymers.

Tubular reactors may also be used in the fluid phase in-line process forblending disclosed herein and more particularly tubular reactors capableof operating up to about 350 MPa. Tubular reactors are fitted withexternal cooling and one or more injection points along the (tubular)reaction zone. As in autoclaves, these injection points serve as entrypoints for monomers (such as propylene), one or more comonomer,catalyst, or mixtures of these. In tubular reactors, external coolingoften allows for increased monomer conversion relative to an autoclave,where the low surface-to-volume ratio hinders any significant heatremoval. Tubular reactors have a special outlet valve that can send apressure shockwave backward along the tube. The shockwave helps dislodgeany polymer residue that has formed on reactor walls during operation.Alternatively, tubular reactors may be fabricated with smooth,unpolished internal surfaces to address wall deposits. Tubular reactorsgenerally may operate at pressures of up to 360 MPa, may have lengths of100-2000 meters or 100-4000 meters, and may have internal diameters ofless than 12.5 cm. Typically, tubular reactors have length-to-diameterratios of 10:1 to 50,000:1 and include up to 10 different injectionpositions along its length.

Reactor trains that pair autoclaves with tubular reactors are alsocontemplated within the scope of the fluid phase in-line process forblending disclosed herein. In this reactor system, the autoclavetypically precedes the tubular reactor or the two types of reactors formseparate trains of a parallel reactor configuration. Such reactorsystems may have injection of additional catalyst and/or feed componentsat several points in the autoclave, and more particularly along the tubelength. In both autoclaves and tubular reactors, at injection, feeds aretypically cooled to near ambient temperature or below to provide maximumcooling and thus maximum polymer production within the limits of maximumoperating temperature. In autoclave operation, a preheater may operateat startup, but not after the reaction reaches steady state if the firstmixing zone has some back-mixing characteristics. In tubular reactors,the first section of double-jacketed tubing may be heated (especially atstart ups) rather than cooled and may operate continuously. Awell-designed tubular reactor is characterized by plug flow wherein plugflow refers to a flow pattern with minimal radial flow rate differences.In both multizone autoclaves and tubular reactors, catalyst can not onlybe injected at the inlet, but also optionally at one or more pointsalong the reactor. The catalyst feeds injected at the inlet and otherinjection points can be the same or different in terms of content,density, and concentration. Catalyst feed selection allows polymerdesign tailoring within a given reactor or reactor train and/ormaintaining the desired productivity profile along the reactor length.

At the reactor outlet valve, the pressure drops to begin the separationof polymer and unreacted monomer, co-monomers, solvents and inerts, suchas for example ethane, propane, hexane, and toluene. More particularly,at the reactor outlet valve, the pressure drops to levels below thatwhich critical phase separation allowing for a polymer-rich phase and apolymer-lean phase in the downstream separation vessel. Typically,conditions remain above the polymer product's crystallizationtemperature. The autoclave or tubular reactor effluent may bedepressurized on entering the downstream high-pressure separator (HPS oralso referred to as a separator, separator vessel, separation vessel,separator/blender vessel, or separation/blending vessel).

As will be subsequently described in detail, the temperature in theseparation vessel is maintained above the solid-fluid phase separationtemperature, but the pressure may be below the critical point. Thepressure need only be high enough such that the monomer may condenseupon contacting standard cooling water. The liquid recycle stream maythen be recycled to the reactor with a liquid pumping system instead ofthe hyper-compressors required for polyethylene units. The relativelylow pressure in separator reduces the monomer concentration in theliquid polymer phase which results in a lower polymerization rate. Thepolymerization rate may be low enough to operate the system withoutadding a catalyst poison or “killer”. If a catalyst killer is required(e.g., to prevent reactions in the high pressure recycle) then provisionmust be made to remove any potential catalyst poisons from the recycledpolymer rich monomer stream for example, by the use of fixed bedadsorbents or by scavenging with an aluminum alkyl.

In an alternative embodiment, the HPS may be operated over the criticalpressure of the monomer or monomer blend but within the densefluid-fluid two phase region, which may be advantageous if the polymeris to be produced with a revamped high-pressure polyethylene (HPPE)plant. The recycled HPS overhead is cooled and dewaxed before beingreturned to the suction of the secondary compressor, which is typical ofHPPE plant operation. The polymer from this intermediate orhigh-pressure vessel then passes through another pressure reduction stepto a low pressure separator. The temperature of this vessel ismaintained above the polymer melting point so that the polymer from thisvessel can be fed as a liquid directly to an extruder or static mixer.The pressure in this vessel is kept low by using a compressor to recoverthe unreacted monomers, etc. to the condenser and pumping systemreferenced above.

In addition to autoclave reactors, tubular reactors, or a combination ofthese reactors, loop-type reactors may be utilized in the fluid phasein-line process for blending disclosed herein. In this reactor type,monomer enters and polymer exits continuously at different points alongthe loop, while an in-line pump continuously circulates the contents(reaction liquid). The feed/product takeoff rates control the totalaverage residence time. A cooling jacket removes reaction heat from theloop. Typically feed inlet temperatures are near to or below ambienttemperatures to provide cooling to the exothermic reaction in thereactor operating above the crystallization temperature of the polymerproduct. The loop reactor may have a diameter of 41 to 61 cm and alength of 100 to 200 meters and may operate at pressures of 25 to 30MPa. In addition, an in-line pump may continuously circulate thepolymerization system through the loop reactor.

The polymerization processes of the fluid phase in-line process forblending polymers disclosed herein may have residence times in thereactors as short as 0.5 seconds and as long as several hours,alternatively from 1 sec to 120 min, alternatively from 1 second to 60minutes, alternatively from 5 seconds to 30 minutes, alternatively from30 seconds to 30 minutes, alternatively from 1 minute to 60 minutes, andalternatively from 1 minute to 30 minutes. More particularly, theresidence time may be selected from 10, or 30, or 45, or 50, seconds, or1, or 5, or 10, or 15, or 20, or 25, or 30 or 60 or 120 minutes. Maximumresidence times may be selected from 1, or 5, or 10, or 15, or 30, or45, or 60, or 120 minutes.

The monomer-to-polymer conversion rate (also referred to as theconversion rate) is calculated by dividing the total quantity of polymerthat is collected during the reaction time by the amount of monomeradded to the reaction. Lower conversions may be advantageous to limitviscosity although increase the cost of monomer recycle. The optimumtotal monomer conversion thus will depend on reactor design, productslate, process configuration, etc., and can be determined by standardengineering techniques. Total monomer conversion during a single passthrough any individual reactor of the fluid phase in-line process forblending disclosed herein may be up to 90%, or below 80%, or below 60%or 3-80%, or 5-80%, or 10-80%, or 15-80%, or 20-80%, or 25-60%, or3-60%, or 5-60%, or 10-60%, or 15-60%, or 20-60%, or 10-50%, or 5-40%,or 10-40%, or 40-50%, or 15-40%, or 20-40%, or 30-40% or greater than5%, or greater than 10%. In one embodiment, when the product isisotactic polypropylene and long-chain branching (LCB) of thepolypropylene is desired (g′≦0.97 based on GPC-3D and using an isotacticpolypropylene standard), single pass conversions may be above 30% andalternatively single-pass conversions may be above 40%. In anotherembodiment, when isotactic polypropylene essentially free of LCB isdesired (0.97<g′<1.05), single-pass conversions may be not higher than30% and alternatively single-pass-conversions may be not higher than25%. To limit the cost of monomer separation and recycling, single-passconversions may be above 3%, or above 5%, or above 10%. It should beunderstood that the above exemplary conversion values reflect totalmonomer conversion, i.e., the conversion obtained by dividing thecombined conversion rate of all monomers by the total monomer feed rate.When monomer blends are used, the conversion of the more reactivemonomer component(s) will always be higher than that of the lessreactive monomer(s). Therefore, the conversion of the more reactivemonomer component(s) can be substantially higher than the totalconversion values given above, and can be essentially complete,approaching 100%.

Product Separation and Downstream Processing:

The base polymer and the optionally in-line-produced plasticizer reactoreffluents of the processes disclosed herein are depressurized to apressure significantly below the cloud point pressure. This allowsseparation of a polymer-rich phase for further purification and amonomer-rich phase for optional separation and recycle compression backto the reactor(s). The base polymer and the optional plasticizer reactoreffluents may be optionally heated before pressure let down to avoid theseparation of a solid polymer phase, which causes fouling of theseparators and associated reduced-pressure lines. The blending of thebase polymer and optional in-line-produced plasticizer containingstreams and the separation of the plasticized polymer-rich phase and themonomer-rich phase in the processes disclosed herein is carried out in avessel known as a high-pressure separator (also referred to as an HPS,separator, separator vessel, or separation vessel). The high-pressureseparator located after the mixing point of the polymer-containingproduct streams and plasticizer-containing product streams of allreactor trains of the parallel reactor bank is also referred to as,separator-blender, separator-blender vessel, or separation-blendingvessel recognizing its dual function of blending the saidpolymer-containing and plasticizer-containing product streams while alsoseparating a monomer-rich phase and solvent-rich phase from aplasticized polymer-rich phase, the latter of which comprises theplasticized polymer blend of the in-line blending processes disclosedherein.

In certain embodiments, single-stream high-pressure separators employedto partially recover the monomer(s) and optional solvent(s) from theeffluent of a single reactor train before sending the polymer-enrichedstream and plasticizer-enriched stream to the downstreamseparator-blender. In such embodiments, the separator-blender blends oneor more base polymer-enriched stream optionally (as in options (1) and(2) of the process examples described earlier) with one or moreunreduced plasticizer reactor train effluent to yield a monomer-richphase and a plasticized polymer-rich phase, the latter of whichcomprises the plasticized polymer blend of the in-line blending processdisclosed herein. In another embodiment, the single-stream high-pressureseparator placed upstream of the separator-blender also functions as abuffer vessel (separator-buffer vessel) by allowing the fluid level ofthe polymer-enriched phase or plasticizer-enriched phase to vary in theseparator-buffer vessel. Such buffering enables a more precise controlof the blend ratios by compensating for the momentary fluctuations inthe production rates in the individual reactor trains of the in-lineblending process disclosed herein.

The plasticized polymer rich phase of the separator-blender may then betransferred to one or more low-pressure separators (LPS also referred toas a low-pressure separation vessel) running at just above atmosphericpressure for a simple flash of light components, reactants and oligomersthereof, for producing a low volatile-containing polymer melt enteringthe finishing extruder or optional static mixer. The one or morelow-pressure separators are distinguished from the one or morehigh-pressure separators in generally operating at lower pressuresrelative to the high-pressure separators. The one or more low-pressureseparators also are located downstream of the one or more high-pressureseparators including the separator-blender. In some embodiments of theprocesses described herein, the plasticized polyolefin-containing streamare mixed with the optional off-line-produced plasticizer and/or otherpolymer additive feeds upstream of or in the low-pressure separator. Aspreviously stated, a high-pressure separator may be alternativelyreferred to herein as an HPS, separator, separator vessel, separationvessel, separator-blender vessel, or separation-blending vessel, orseparator-blender even if some blend components are introduced in thelow-pressure separator section of the in-line blending processesdisclosed herein. The use of the term “pressure” in conjunction withlow-pressure separator and high-pressure separator is not meant toidentify the absolute pressure levels at which these separators operateat, but is merely intended to given the relative difference in pressureat which these separators operate. Generally, separators locateddownstream in the in-line blending processes disclosed herein operate atlower pressure relative to separators located upstream.

In one embodiment of the fluid phase in-line process for blendingpolymers disclosed herein, polymerization is conducted in two or morereactors of a type described herein above under agitation and above thecloud point for the polymerization system. Then, the polymer-monomermixtures are transferred into a high-pressure separation-blendingvessel, where the pressure is allowed to drop below the cloud point.This advantageously results in the denser, polymer-rich phase separatingfrom the lighter monomer-rich phase. As may be appreciated by thoseskilled in the art, it may optionally be necessary to increase thetemperature before or in the high-pressure separation vessel to preventthe formation of a solid polymer phase as the polymer becomes moreconcentrated. The monomer-rich phase is then separated and recycled tothe reactors while the polymer-rich phase is fed to a coupleddevolatilizer—such as a LIST dryer (DTB) or devolatizing extruder.

The recycle runs through a separator, where the pressure depends on thepressure-temperature relationship existing within the reactor. Forexample, supercritical propylene polymerization can be carried out underagitation in the single-phase region in the reactor at 40-200 MPa and95-180° C. (see FIG. 23). The product mixture can be discharged into aseparator vessel, where the pressure is dropped to a level of 25 MPa orlower, in which case, the mixture is below its cloud point, while themonomer has not yet flashed off (again, see FIG. 23). Under suchconditions, it would be expected from Radosz et al., Ind. Eng. Chem.Res. 1997, 36, 5520-5525 and Loos et al., Fluid Phase Equil. 158-160,1999, 835-846 that the monomer-rich phase would comprise less than about0.1 wt % of low molecular weight polymer and have a density ofapproximately 0.3-0.7 g/mL (see FIG. 24). The polymer-rich phase wouldbe expected to have a density of approximately 0.4-0.8 g/mL.

Assuming that the pressure is dropped rapidly enough, for example,greater than or equal to about 6 MPa/sec, the phases will separaterapidly, permitting the recycle of the monomer-rich phase as a liquid,without the issue of having the monomer-rich phase return to the gasphase. As may be appreciated by those skilled in the art, thiseliminates the need for the energy-intensive compression andcondensation steps.

The plasticized polymer-rich phase is sent directly to a coupleddevolatilizer. Suitable devolatilizers may be obtained, for example,from LIST USA Inc., of Charlotte, N.C. The devolatilization is aseparation process to separate remaining volatiles from the finalplasticized polymer, eliminating the need for steam stripping. Workingunder low vacuum, the polymer solution flashes into the devolatilizer,exits the unit and is then transferred on for further processing, suchas pelletization.

Any low or very low molecular weight polymer present in the monomer-richphase to be recycled may optionally be removed through “knock-out” pots,standard hardware in reactors systems, or left in the return streamdepending upon product requirements and the steady-state concentrationof the low molecular weight polymer fraction in the product.

In solution reactor processes, present practices employed by thoseskilled in the art typically effect separation by flashing monomer andsolvent or accessing the high-temperature cloud point.

In another form, polymerization is conducted at conditions below thecloud point, with the polymer-monomer mixture transported to agravimetric separation vessel, where the pressure could be furtherlowered if desired to enhance phase separation of the polymer-rich andmonomer-rich phases. In either of the forms herein described, themonomer, for example, propylene, is recycled while staying in arelatively high density, liquid-like (dense supercritical fluid or bulkliquid) state. Once again, one or more knock-out pots may be employed toaid in the removal of low molecular weight polymer from the recyclestream.

As may be appreciated, there are possible and optimal operating regimesfor the polymer blend and plasticizer blend component reactors and forthe gravity (lower critical solution temperature (LCST)) separator.Referring now to FIG. 25, for reactors operating in a single liquidphase regime, a possible region for operation is just above the LCST andvapor pressure (VP) curves. The optimal region (shown within the shadedoval) for operation occurs at temperatures just above the lower criticalend point (LCEP) and at pressures slightly above the LCST curve.

Referring now to FIG. 26, for reactors operating within a two-phasefluid-fluid regime, the possible region for operation occurs basicallyanywhere below the LCST curve. The optimal region (again, shown withinthe shaded oval) occurs just below the LCST and above the VP curve,although, as may be appreciated, many factors could have a bearing onwhat actually is optimal, such as the final properties of the desiredproduct. As recognized by those skilled in the art, the two-phaseliquid-liquid regime is the economically advantageous method ifpolypropylene is to be produced with a revamped HPPE plant.

Referring now to FIG. 27, for the case where polymerization is conductedat conditions below the cloud point and the polymer-monomer mixturetransported to a gravimetric LCST separator, the possible region ofoperation is anywhere below the LCST curve and above the VP curve. Theoptimal region (again, shown within the shaded oval) occurs within thatportion that is below the spinodal, but not too low in pressure, asshown. Operating in this regime assures that the energy use isoptimized. It is also desirable to avoid operation in the region betweenthe LCST and spinodal curves in order to obtain good gravity settlingperformance. Moreover, it is desirable that the separation is effectedat sufficiently high temperatures, so that crystallization does notoccur in the polymer-rich phase. This may require that the temperatureof the mixture in the separator be higher than the temperature in thereactor(s).

Advantageously, the liquid monomer-rich recycle stream can be recycledto the reactor using a liquid pumping system instead of ahyper-compressor, required for conventional polyethylene units.

In another embodiment of the invention, polymerization is as describedin WO2004/026921, and with the pressure above the cloud point pressurefor the polymerization medium. The polymerization medium is continuouslytransferred without heating to a pressure reducing device (which may bea letdown valve), where the pressure is reduced below the cloud pointpressure. This advantageously results in the formation of a denser,polymer-rich phase and a less dense monomer-rich phase, which are thentransferred to a fluid-liquid separation vessel called a High PressureSeparator (HPS), where the monomer-rich phase and polymer-rich phaseform and separate into two layers via gravity settling.

In another embodiment, it may be necessary to increase the temperatureof the polymerization medium by a heating device located upstream of thepressure reducing device (letdown valve) to prevent a solid-liquid phasetransition (crystallization) of the polymer-rich phase in the HPS, whichcould occur as the polymer concentration increases, or to allowoperation of the HPS at a higher pressure and thereby avoid full orpartial vaporization of the monomer-rich phase. The monomer-rich phaseis then recycled from the top of the HPS to the reactor while thepolymer-rich phase is fed to optional low-pressure phase separators(LPS) placed downstream of the first phase separator, and ultimately toa coupled devolatilizer—such as a LIST dryer (DTB) or devolatizingextruder. The operating pressures of the separators are decreasing inthe separator cascade causing the polymer-rich phase in a downstreamseparator to become more concentrated in the polymer and depleted in thelight components of the polymerization system such as monomers andoptional inert solvents diluents as compared to the corresponding phaseconcentrations upstream.

Phase Separation Temperature:

In all embodiments of the current invention, the optional heating of thepolymerization medium upstream of the pressure letdown device isminimized within the constraints imposed by the phase diagram for thepolymerization medium. For efficient phase separation, the temperatureof the polymerization medium at the entrance to the pressure reducingdevice (letdown valve) must be high enough to prevent a solid-liquidphase separation from taking place upstream of, or inside, thefluid-liquid phase separation vessel (HPS). The efficient phaseseparation temperature must also be high enough such that when thepressure is reduced across the pressure reducing device (letdown valve),that there exists a pressure where an efficient separation of thepolymerization medium into a monomer-rich phase and a polymer-rich phasecan occur at a high enough pressure to prevent full or partialvaporization of the monomer-rich phase. The applicable operating rangeof temperatures and pressures that satisfy these criteria may bedetermined from a T,P phase diagram of the polymerization medium of thetype depicted in FIG. 29. Because heating of the polymerization mediumincreases investment costs (installation of heaters), and also increasesoperating cost (consumption of a heating utility), the preferredembodiments of the process generally employ no heating if thepolymerization system is already operating at a temperature that exceedsthe efficient phase separation temperature criteria. Alternatively,embodiments where the polymerization medium is at a temperature lowerthan that required to satisfy the efficient phase separation criteriawill employ minimal heating to raise the temperature at the inlet of thepressure reducing device (letdown valve) to 0-100° C., or 5-50° C., or10-30° C. above minimum required temperature for efficient phaseseparation.

In consideration of the efficient phase separation temperature criteria,the process of the current invention can be carried out at the followingtemperatures. In one embodiment, the temperature of the polymerizationsystem is above the solid-fluid phase transition temperature of thepolymer-containing fluid reaction medium at the reactor pressure,preferably at least 5° C. above the solid-fluid phase transitiontemperature of the polymer-containing fluid reaction medium at thereactor pressure, more preferably, at least 10° C. above the solid-fluidphase transformation point of the polymer-containing fluid reactionmedium at the reactor pressure. In another embodiment, the temperatureis between 50 and 350° C., or between 60 and 250° C., or between 70 and200° C., or between 80 and 180° C., or between 90 and 160° C., orbetween 100 and 140° C.

Spinodal Decomposition:

In preferred embodiments of the current invention, the pressure reducingdevice is designed to drop the pressure rapidly enough, and to anoptimal pressure, via the process of spindoal decomposition, whichresults in a phase morphology of an interpenetrating network of the twophases (also called a co-continuous morphology), with the desirableresult that the polymer-rich and monomer-rich phases disengage easilyand settle rapidly in the fluid-liquid gravity separation vessel (HPS).Spinodal decomposition prevents the formation of a very slow disengagingand slow settling mixture of monomer-rich and polymer-rich phases with amorophology that has droplets of monomer-rich phase dispersed in acontinuous polymer-rich phase, which tends to occur naturally when thepolymer concentration in the fluid exceeds a critical value, and whentemperature and pressure in the phase separating vessel are in theregion of the phase diagram between the fluid-liquid phase boundary(bindoal boundary) and the spindoal boundary as illustrated by thecross-hatched area in FIG. 29. In the preferred embodiments of thecurrent invention, the polymer concentration in the polymerizationmedium is always higher than the critical concentration described above(and conceptually illustrated in FIG. 28) and thus these embodimentsutilize the process of spindoal decomposition to avoid gravity settlingproblems. In one embodiment of the spinodal decomposition process forpolymerization systems described in WO2004/026921, the rate of pressurereduction across the pressure reducing device (letdown valve) is 1MPa/sec or more, or 2 Mpa/sec or more, or 4 MPa/sec or more, or 6MPa/sec or more.

Phase Separation Pressure:

In all embodiments of the current invention, the pressure downstream ofthe pressure reducing device (letdown valve) and inside the fluid-liquidphase separation vessel (HPS) is selected to be below the cloud pointpressure to ensure that a fluid-liquid phase separation will take place,but high enough to be above the vapor pressure of the monomer-rich phaseto prevent full or partial vaporization of the monomer-rich phase. Inpreferred embodiments, to induce rapid phase separation and settling,the pressure in the fluid-liquid phase separation vessel (HPS) is lowerthan the spinodal boundary pressure. Within this preferred pressurerange, ie. below the spinodal boundary pressure and above the vaporpressure of the monomer-rich phase, an operating pressure can be chosenthat will prove to be most economical. Higher pressures reduce the costof pumping or compression of the monomer-rich phase for recycle, buthigher pressures also reduce the rate of phase disengagement and resultin higher density of the monomer-rich phase, which reduces the densitydifference between polymer-rich and monomer-rich phases, thereby slowingthe rate of settling in the fluid-liquid phase separation vessel (HPS),and ultimately requiring a larger HPS vessel. Thus, at someexperimentally determined pressure within the preferred pressure range,the lowest total cost of pumping/compression and HPS vessel size will beachieved. In one embodiment of the invention, the pressure downstream ofthe pressure reducing device (letdown valve) and inside the fluid-liquidphase separation vessel (HPS) is below the spinodal boundary pressure,or at least 1 MPa lower than the spinodal boundary pressure, or at least5 MPa lower than the spinodal boundary pressure, or at least 10 MPalower than the spinodal boundary pressure. In one embodiment, thepressure is no lower than the vapor pressure of monomer-rich phase, nolower than 0.2 MPa above, no lower than 1 MPa above, or no lower than 10MPa above the vapor pressure of the monomer-rich phase. In anotherembodiment, the difference in density between the polymer-rich phase andthe monomer-rich phase is 0.1 g/mL, or 0.2 g/mL, or 0.4 g/mL, or 0.6g/mL. In another embodiment, the pressure is between 2 and 40 MPa, 5 and30 MPa, 7 and 20 MPa, or between 10 and 18 MPa.

Polymer Recovery:

The polymer-rich phase may be sent directly to a coupleddevolatilization system, which may be comprised of one or more flashvessels, low pressure separators (LPS), in series, each operating at asuccessively lower pressure, and said devolatization system may includeas a final step a devolatizing extruder or other devolatizing devicessuch as a LIST DTB, which may be obtained from LIST USA Inc., ofCharlotte, N.C. The low pressure separator vessel(s) may operateadiabatically, or optionally may have internal heaters of the thin filmor falling strand type. This devolatilization is a separation process toseparate remaining volatiles from the final polymer, without resortingto older, inefficient processes such as steam stripping. The finaldevolatizing device (extruder, LIST DTB, etc.) may operate under astrong vacuum, and may optionally use stripping agents such as water ornitrogen, to further reduce the volatiles content of the polymer. Oncedevolatized, the product exits the final devolatizing step and is thentransferred on for further processing, such as pelletization andpackaging.

Efficient and Economical Recycle of Monomer-Rich Phase:

In preferred embodiments of the invention, the monomer-rich phase isrecycled to the polymerization system with minimal processing to avoidcostly investment in recycle equipment, and also to avoid consumption ofcostly utilities including heating media (steam, hot oil, electricity,etc.) and cooling media (cooling water, brine, cooling air, etc.). Inembodiments where the temperature of the monomer-rich phase in thefluid-liquid separation vessel (HPS) is higher than the polymerizationsystem feed temperature, some cooling of the monomer-rich phase will berequired. If removal of water or other polar contaminants is notrequired to maintain an economical catalyst productivity in thepolymerization system, then cooling of the monomer-rich recycle streamto the polymerization system feed temperature may be all that isrequired. One embodiment of this type involves cooling the monomer-richrecycle stream to −40 to 100° C., or −20 to 90° C., or 0 to 90° C., or20 to 90° C., or 50 to 90° C. Where removal of water or polarcontaminants is required to maintain an economical catalyst productivityin the polymerization system, then drying over desiccant beds may beused, and the monomer-rich recycle stream must be a cooled to the lowerof the polymerization feed temperature or the temperature where thedesiccant has an acceptable capacity for removing water and/or otherpolar impurities (eg. catalyst poisons). In this case where desiccantdrying is required, one embodiment involves cooling the monomer-richrecycle stream to −40 to 80° C., or −20 to 60° C., or 0 to 40° C., or 20to 40° C. When cooling the monomer-rich recycle stream, low or very lowmolecular weight polymer present in the monomer-rich stream mayprecipitate as solids, which may optionally be removed through filters,“knock-out” pots, etc. or left in the return stream depending uponproduct requirements and the steady-state concentration of the lowmolecular weight polymer fraction in the product.

Heat Integration:

In embodiments of the invention where heating of the polymerizationmedium and cooling of the monomer-rich recycle stream are both required,it is often advantageous to install a heat integrating exchanger, whichwill be defined as any device that exchanges heat between themonomer-rich phase leaving the fluid-liquid separator and thepolymerization medium upstream of the pressure reducing device. Thisexchange of heat simultaneously heats the polymerization medium andcools the monomer-rich recycle stream. In embodiments where thisexchange of heat is insufficient to raise the polymerization medium toits desired temperature and/or to cool the monomer-rich recycle streamto its desired temperature, supplemental heating and cooling systems maybe employed in conjunction with the heat integrating exchanger. In suchembodiments, preferred heating media for the polymerization mediuminclude, but are not restricted to, steam, hot oil systems, and electricheater systems. Preferred supplemental cooling media for themonomer-rich recycle stream include, but are not restricted to, freshwater cooling systems, salt water cooling systems, air-cooledexchangers, and the like.

Application to Two-Phase Polymerization System:

In another embodiment of the invention, the polymerization system ofWO2004/026921 is operated at a pressure below the cloud point pressure,with the two phase (fluid-liquid) polymerization medium transporteddirectly to a gravimetric separation vessel, optionally by way of apressuring reducing device where the pressure may be further lowered ifdesired to enhance phase separation of the polymer-rich and monomer-richphases. In this embodiment, the monomer-rich phase is recycled to thepolymerization system in the same manner as described for apolymerization system operating above the cloud point pressure. Otheraspects of the current invention, including spinodal decomposition,supplemental cooling of the monomer-rich recycle stream, desiccantdrying of the monomer-rich recycle stream, removal of low molecularweight polymer that precipitates from the monomer-rich recycle stream,hydrogen removal, and catalyst killing may also be employed in thisembodiment.

Hydrogen Removal from Monomer-Rich Recycle Stream:

Many of the catalyst systems of the polymerization system ofWO2004/026921, and thus of the current invention, produce small amountsof hydrogen as a byproduct of the polymerization reaction. Additionally,hydrogen is disclosed as one of the possible reactor feeds for thispolymerization process. For these two reasons, in all embodiments of thepolymerization process where the hydrogen is not totally consumed in thepolymerization process, there will be small amounts of hydrogen in thepolymerization medium, and most of this hydrogen will remain in themonomer-rich phase leaving the fluid-liquid phase separation vessel(HPS). In one embodiment, this amount of hydrogen in the monomer-richrecycle stream is less than the amount of hydrogen added to the combinedfeed stream to the polymerization process, and in this embodiment, thefresh makeup of hydrogen to the polymerization process feed can bereduced to compensate for this recycled hydrogen, and no furtherprocessing of the monomer-rich recycle stream to remove hydrogen isrequired. In another embodiment, the amount of hydrogen in themonomer-rich recycle stream is greater than the total amount of hydrogendesired in the combined feed stream to the polymerization process, andin this embodiment, an additional treatment step may be added to theprocess for recycling the monomer-rich phase. This additional treatmentstep may comprise, but is not restricted to, single or multiple stageflash vessels, fractionation towers, or hydrogenation beds. Treatmentfor removal of hydrogen may be applied to the entire monomer-richrecycle stream, or in instances where the hydrogen removal requirementspermit, to only a portion, or slip-stream of the monomer-rich recyclestream.

Catalyst Killing:

The use of the processes disclosed herein and the relatively lowpressure in the separator vessel greatly reduces the monomerconcentration in the liquid polymer-rich phase, which, in turn, resultsin a much lower polymerization rate. This polymerization rate may be lowenough to operate this system without adding a catalyst poison or“killer”. If no killing compounds are added then the killer removal stepmay be eliminated.

If a catalyst killer is required, then provision must be made to removeany potential catalyst poisons from the recycled monomer-rich stream(e.g. by the use of fixed bed adsorbents or by scavenging with analuminum alkyl). The catalyst activity may be killed by addition of apolar species. Non-limiting exemplary catalyst killing agents includewater, alcohols (such as methanol and ethanol), sodium/calcium stearate,CO, and combinations thereof. The choice and quantity of killing agentwill depend on the requirements for clean up of the recycle propyleneand comonomers as well as the product properties, if the killing agenthas low volatility. The catalyst killing agent may be introduced intothe polymer blend and plasticizer blend component reactor effluentstream after the pressure letdown valve, but before the HPS. The choiceand quantity of killing agent may depend on the requirements for cleanup of the recycle propylene and comonomers as well as the productproperties, if the killing agent has low volatility.

Base Polymer Blending Components:

The base polymer and plasticizer blending components produced by thein-line blending processes disclosed herein may have any type of chainarchitecture, including, but not limited to, block, linear, radial,star, branched, hyperbranched, dendritic, and combinations thereof.Exemplary base polymers include, high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),very low density polyethylene (vLDPE), isotactic polypropylene (iPP),syndiotactic polypropylene (sPP), ethylene-propylene random copolymerstypically containing less than 10 wt % ethylene (RCPs),ethylene-propylene plastomers typically containing 65-85 wt % ethylene,ethylene-propylene elastomers typically containing 10-20 wt % ethylene,impact copolymers of ethylene and propylene (ICPs), ethylene-propylenerubbers (EPRs), ethylene-propylene-diene terpolymers (EPDs),ethylene-propylene-butene-1 (EPB) terpolymers, olefin block copolymers,poly(1-butene), styrenic block copolymers, butyl, halobutyl,thermoplastic vulcanizers, and blends thereof. Advantageously, the basepolymer comprises isotactic polypropylene or ethylene-propylene randomcopolymers.

Some forms produce polypropylene and copolymers of polypropylene with aunique microstructure. The processes disclosed herein can be practicedsuch that novel isotactic and syndiotactic compositions are made. Inother forms, low crystallinity polymers are made.

In other forms, the copolymer includes from 90 to 99.999 weight % ofpropylene units, from 0.000 to 8 weight % of olefin units other thanpropylene units and from 0.001 to 2 weight % α,ω-diene units. Copolymerforms may have weight-average molecular weights from 20,000 to2,000,000, crystallization temperatures (without the addition ofexternal nucleating agents) from 115° C. to 135° C. and melt flow rates(MFRs) from 0.1 dg/min to 100 g/10 min. The accompanying olefin may beany of C₂-C₂₀ α-olefins, diolefins (with one internal olefin) and theirmixtures thereof. More specifically, olefins include ethylene, butene-1,pentene-1, hexene-1, heptene-1,4-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 1-decene, 1-undecene,and 1-dodecene.

Plasticizer copolymers of propylene made under supercritical conditionsinclude ethylene and C₄-C₁₂ comonomers such asbutene-1,3-methylpentene-1, hexene-1,4-methylpentene-1, and octene-1.The in-line blending processes disclosed herein can prepare thesecopolymers without the use of solvent or in an environment with lowsolvent concentration.

Propylene-based polymers produced typically comprise 0 to 60 weight % ofa comonomer, or 1 to 50 weight %, or 2 to 40 weight %, or 4 to 30 weight%, or 5 to 25 weight %, or 5 to 20 weight %, and have one or more of:

-   -   1. a heat of fusion, ΔH_(f), of 30 J/g or more, or 50 J/g or        more, or 60 or more, or 70 or more, or 80 or more, or 90 or        more, or 95 or more, or 100 or more, or 105 or more or an ΔH_(f)        of 30 J/g or less, or 20 J/g or 0;    -   2. a weight-averaged molecular weight (as measured by GPC DRI)        of 20,000 or more, or 30,000 to 1,000,000, or 50,000 to 500,000,        or 50,000 to 400,000;    -   3. a melt flow rate of 0.1 g/10 min or more, or 0.5 g/10 min or        more, or 1.0 g/10 min or more, or between 0.1 and 10,000 g/10        min;    -   4. a melting peak temperature of 55° C. or more, or 75° C. or        more, or 100° C. or more, or 125° C. or more, or 150° C. or        more, between 145 and 165° C.;    -   5. an M_(w)/M_(n) (as measured by GPC DRI) of about 1.5 to 20,        or about 1.5 to 10, or 1.8 to 4.

In another form, the polymer blend components produced by the in-lineblending processes disclosed herein have a melt viscosity of less than10,000 centipoises at 180° C. as measured on a Brookfield viscometer, orbetween 1000 to 3000 cP for some forms (such as packaging and adhesives)or between 5000 and 10,000 cP for other applications.

Plasticizer Blending Components:

The plasticizer blend component is any compound which improvesparticular properties of the in-line produced plasticized polymer blenddirected towards softness, impact strength (e.g., Gardner impact),toughness, flexibility (e.g., lower flexural modulus), and orprocessability (e.g., higher melt flow) and the like. In certainembodiments, the plasticizer blend component has a lower glasstransition temperature (Tg) than the base polymer, such that the Tg ofthe plasticized polymer blend is lower than the Tg of the base polymer.In other embodiments, the plasticizer has a lower crystallinity than thebase polymer, such that the total crystallinity of the plasticizedpolymer blend is lower than the crystallinity of the base polymer.Advantageous plasticizers are characterized in that, when blended withthe base polymer to form a blend, the plasticizer and the polymer form ahomogeneous composition, also referred to as a homogeneous blend.Advantageously, the plasticizer is miscible with the one or morepolymers, as indicated by no change in the number of peaks in theDynamic Mechanical Thermal Analysis trace (DMTA), as compared to theDMTA trace of the one or more polymers in the absence of theplasticizer.

It should be understood that any plasticizer component conducive toin-line production and in-line blending may also be produced off-lineand then blended in-line. However, plasticizer components that are notconducive to in-line production, advantageously are produced off-lineand then are blended in-line.

I. In-Line-Produced In-Line Blended Plasticizers

Advantageous plasticized polymer blends are composed of a blend of oneor more high molecular weight base polymer blend components and one ormore plasticizer blend components. One or more the plasticizer blendcomponents for the in-line blending process may be produced (formed,reacted) in-line, i.e., in a one or more reactor trains parallel to theone or more reactor trains that polymerize the high molecular weightpolymer components. The one or more plasticizers polymerized in-line arethen subsequently in-line blended with the one or more high molecularweight polymer components. Non-limiting exemplary plasticizers forin-line reacting and blending with one or more high molecular weightpolymers include polyolefin oligomers and soft polyolefins.

I.A. In-Line-Produced In-Line Blended Soft Polyolefin Plasticizers

The in-line produced plasticizer may comprise, or may consistessentially of one or more soft polyolefins acting as plasticizers thatare either produced in-line, off-line or a combination thereof (i.e. oneor more soft polyolefin produced in-line and one or more softpolyolefins produced in an off-line process, outside the processboundary of the disclosed processes). If produced off-line, the one ormore soft polyolefins are in-line blended from one or morepolymer/additive storage tanks with the plasticized polymer blendcomponents of the in-line blending process disclosed herein. In anadvantageous embodiment, the one or more soft polyolefins are reactedin-line and subsequently blended in-line with the one or more highmolecular weight polyolefin components, which avoids the necessity forone or more separate polymer/additive storage tanks dedicated for softpolyolefins.

In one embodiment, the soft polyolefin plasticizers have a density of0.88 g/mL or less, more preferably 0.87 g/mL or less, most preferably0.86 g/mL or less. In another embodiment, the soft polyolefinplasticizers has a weight % crystallinity of 15% or less, preferably 10%or less, preferably 5% or less. In another embodiment, the softpolyolefin plasticizers comprise at least 50 mole % ethylene and has aweight % crystallinity of 15% or less, preferably 10% or less,preferably 5% or less. In yet another embodiment, the soft polyolefincomprises at least 50 mole % propylene and has a weight % crystallinityof 25% or less, preferably 20% or less, preferably 15% or less. Suitableethylene copolymers have a weight-averaged molecular weight (Mw) of 0.5to 10 kg/mol, a weight-/number-averaged molecular weight ratio (Mw/Mn)of 1.5 to 3.5, and a comonomer content of 20 to 70 mol %. Comonomers forthe said ethylene copolymers are selected from C₃ to C₂₀ linear orbranched alpha-olefins and diolefins. Specific examples of ethylenecopolymers include, but are not limited to, ethylene-propylene,ethylene-butene, ethylene-hexene, and ethylene-octene copolymers. In oneembodiment, the ethylene copolymer desirably has a Tg of from −80 to−30° C., or from −75 to −40° C., or from −70 to −45° C. In anotherembodiment, the ethylene copolymer has an ethylene crystallinity, asdetermined by DSC, of less than 10%, or less than 5%.

In one embodiment, the soft polyolefin plasticizer may comprise, orconsist essentially of one or more ethylene-rich soft polyolefin. Inanother embodiment, the soft polyolefin plasticizer may comprise, or mayconsist essentially of one or more propylene-rich soft polyolefin. Inanother embodiment, the soft polyolefin plasticizer may comprise, orconsist essentially of one or more butene-1-rich soft polyolefin.

I.B. In-Line-Produced In-Line Blended Polyolefin Oligomer Plasticizers

In one embodiment, the plasticizer may comprise, or may consistessentially of one or more polyolefin oligomers that are either producedin-line, off-line or a combination thereof (i.e. one or more type ofpolyolefin oligomer reacted in-line and one or more type of polyolefinoligomer reacted in an off-line process). If produced off-line, the oneor more polyolefin oligomers are in-line blended from one or moreadditive storage tanks with the plasticized polymer blend components ofthe in-line blending process disclosed herein. In an advantageousembodiment, the one or more polyolefin oligomers are reacted in-line andsubsequently blended in-line with the one or more base polyolefincomponents, which avoids the necessity for one or more separate additivestorage tanks dedicated for the polyolefin oligomers.

In another embodiment, the polyolefin oligomers have a density of lessthan 0.90 g/cm³, or less than 0.89 g/cm³, or less than 0.88 g/cm³, orless than 0.87 g/cm³, or less than 0.86 g/cm³.

In another embodiment, the polyolefin oligomers have a H_(f) of lessthan 70 J/g, or less than 60 J/g, or less than 50 J/g, or less than 40J/g, or less than 30 J/g, or less than 20 J/g, or less than 10 J/g, orless than 5 J/g, or the Hf can not be reliably measured.

I.B.1. In-Line-Produced In-Line Blended Ethylene-Based PolyolefinOligomer Plasticizers

The polyolefin oligomer plasticizer may comprise C₁₀ to C₂₀₀₀, or C₁₅ toC₁₅₀₀, or C₂₀ to C₁₀₀₀, or C₃₀ to C₈₀₀, or C₃₅ to C₄₀₀, or C₄₀ to C₂₅₀oligomers (dimers, trimers, etc.) manufactured by the catalyticpolymerization of ethylene and optionally one or more C₃ to C₂₀alpha-olefins. Ethylene-based polyolefin oligomers comprise greater than50 wt % ethylene.

In one embodiment, the ethylene-based polyolefin oligomers comprisegreater than 60 wt % ethylene, or greater than 70 wt % ethylene, orgreater than 80 wt % ethylene, or greater than 90 wt % ethylene, or 100wt % ethylene.

I.B.2. In-Line-Produced In-Line Blended Propylene-Based PolyolefinOligomer Plasticizers

The polyolefin oligomer plasticizer may comprise C₁₀ to C₂₀₀₀, or C₁₅ toC₁₅₀₀, or C₂₀ to C₁₀₀₀, or C₃₀ to C₈₀₀, or C₃₅ to C₄₀₀, or C₄₀ to C₂₅₀oligomers (dimers, trimers, etc.) manufactured by the catalyticpolymerization of propylene and optionally one or more C₅ to C₂₀alpha-olefins. Propylene-based polyolefin oligomers comprise greaterthan 50 wt % propylene.

In one embodiment, the propylene-based polyolefin oligomers comprisegreater than 60 wt % propylene, or greater than 70 wt % propylene, orgreater than 80 wt % propylene, or greater than 90 wt % propylene, or100 wt % propylene.

I.B.3. In-Line-Produced In-Line Blended Butene-Based Polyolefin OligomerPlasticizers

The polyolefin oligomer plasticizer may comprise C₁₀ to C₂₀₀₀, or C₁₅ toC₁₅₀₀, or C₂₀ to C₁₀₀₀, or C₃₀ to C₈₀₀, or C₃₅ to C₄₀₀, or C₄₀ to C₂₅₀oligomers (dimers, trimers, etc.) manufactured by the catalyticpolymerization of butene olefins, including 1-butene, 2-butene, andisobutylene, and optionally one or more olefins selected from C₅ to C₂₀alpha-olefins.

In one embodiment, the polyolefin oligomer comprises a “polybutenes”liquid, which comprises oligomers of C₄ olefins (including 1-butene,2-butene, isobutylene, and butadiene, and mixtures thereof) and up to 10wt % other olefins, and most often comprises primarily isobutylene and1-butene. As used herein, the term “polybutenes” also includeshomopolymer oligomers of isobutylene or 1-butene, copolymer oligomers ofa C₄ raffinate stream, and copolymer oligomers of C₄ olefins with aminority amount of ethylene and/or propylene and/or C₅ olefins.Polybutenes are described in, for example, SYNTHETIC LUBRICANTS ANDHIGH-PERFORMANCE FLUIDS, L. R. Rudnick & R. L. Shubkin, eds., MarcelDekker, 1999, p. 357-392.

Preferred polybutenes include those in which isobutylene derived unitscomprise 40 to 100 wt % (preferably 40 to 99 wt %, preferably 40 to 96wt %) of the polymer; and/or the 1-butene derived units comprise 0 to 40wt % (preferably 2 to 40 wt %) of the copolymer; and/or the 2-butenederived units comprise 0 to 40 wt % (preferably 0 to 30 wt %, preferably2 to 20 wt %) of the polymer.

Suitable polybutenes may have a kinematic viscosity at 100° C. of 3 to50,000 cSt (more commonly 5 to 3000 cSt), a pour point of −60 to 10° C.(more commonly −40 to 0° C.), and a number-average molecular weight of300 to 10,000 g/mol (more commonly 500 to 2,000 g/mol).

Desirable polybutenes liquids are commercially available from a varietyof sources including Innovene (Indopol™ grades) and Infineum (C-Seriesgrades). When the C₄ olefin is exclusively isobutylene, the material isreferred to as “polyisobutylene” or PIB. Commercial sources of PIBinclude Texas Petrochemical (TPC Enhanced PIB grades). When the C₄olefin is exclusively 1-butene, the material is referred to as“poly-n-butene” or PNB. Properties of some polybutenes liquids made fromC₄ olefin(s) are summarized in the table below.

Commercial Examples of Oligomers of C₄ olefin(s) KV @ Pour Flash 100°C., Point, Specific Point, Grade cSt VI ° C. gravity ° C. TPC 137 (PIB)6 132 −51 0.843 120 TPC 1105 (PIB) 220 145 −6 0.893 200 TPC 1160 (PIB)660 190 +3 0.903 230 Innovene Indopol H-25 52  87 −23 0.869 ~150Innovene Indopol H-50 108  90 −13 0.884 ~190 Innovene Indopol H-100 218121 −7 0.893 ~210 Infineum C9945 11  74* −34 0.854 170 Infineum C9907 78103* −15 0.878 204 Infineum C9995 230 131* −7 0.888 212 Infineum C9913630 174* +10 0.888 240 *Estimated based on the kinematic viscosity at100° C. and 38° C.

1.B.4. In-Line-Produced In-Line Blended Higher-Alphaolefin-BasedPolyolefin Oligomer Plasticizers

In one or more embodiments, the polyolefin oligomer plasticizercomponent comprises C₁₀ to C₂₀₀₀, or C₁₅ to C₁₅₀₀, or C₂₀ to C₁₀₀₀, orC₃₀ to C₈₀₀, or C₃₅ to C₄₀₀, or C₄₀ to C₂₅₀ oligomers (dimers, trimers,etc.) manufactured by the catalytic polymerization of C₅— to C₂₀alpha-olefins. Such polyolefin oligomers are “polyalphaolefin” or “PAO”fluids, or simply “PAO”.

PAO fluids (or simply, PAOs) are described in, for example, U.S. Pat.Nos. 3,149,178; 4,827,064; 4,827,073; 5,171,908; and 5,783,531 and inSYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS, Leslie R.Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999, p. 3-52. PAOsare high purity hydrocarbons, with a fully paraffinic structure and ahigh degree of branching. PAO liquids can be conveniently prepared bythe oligomerization of alpha-olefins in the presence of a polymerizationcatalyst, including Lewis acid catalysts such as aluminum trichlorideand polyolefin polymerization catalysts such as Ziegler-Natta catalysts,metallocene or other single-site catalysts, and chromium catalysts.

In one or more embodiments, the PAO comprises oligomers of C₅ to C₁₈, orC₆ to C₁₄, or C₈ to C₁₂ alpha-olefins. The use of linear alpha-olefins(LAOs) is advantageous and the use of C₈ to C₁₂, are particularlyadvantageous. Suitable LAOs include 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,1-tetradecene, 1-pentadecene, 1-hexadecene, and blends thereof.

In one or more embodiments, the PAO comprises oligomers of two or moreC₅ to C₁₈ LAOs, to make ‘bipolymer’ or ‘terpolymer’ or higher-ordercopolymer combinations. An advantageous embodiment involvesoligomerization of a mixture of LAOs selected from C₆ to C₁₈ LAOs witheven carbon numbers. Another advantageous embodiment involvesoligomerization of 1-octene, 1-decene, and 1-dodecene.

In one or more embodiments, the PAO comprises oligomers of a singlealpha-olefin species having a carbon number of 5 to 24, or 6 to 18, or 8to 12, or 10. Oligomers of a single alpha-olefin species having a carbonnumber of 10 are advantageous. In one or more embodiments, the NFPcomprises oligomers of mixed alpha-olefins (i.e., two or morealpha-olefin species), each alpha-olefin having a carbon number of 5 to24, or 6 to 18, or 8 to 12. In one or more embodiments, the PAOcomprises oligomers of mixed alpha-olefins (i.e., involving two or morealpha-olefin species) where the weighted average carbon number for thealpha-olefin mixture is 6 to 14, or 8 to 12, or 9 to 11. Mixedalpha-olefins with weighted average carbon number for the alpha-olefinmixture of 8 to 12, or 9 to 11 are advantageous, and with weightedaverage carbon number for the alpha-olefin mixture of 9 to 11 areparticularly advantageous.

In one or more embodiments, the PAO comprises oligomers of one or morealpha-olefin with repeat unit formulas of —[CHR—CH₂]— where R is a C₃ toC₁₈ saturated hydrocarbon branch. In one or more embodiments, R isconstant for all oligomers. In one or more embodiments, there is a rangeof R substituents covering carbon numbers from 3 to 18. Advantageously,R is linear, i.e., R is (CH₂)_(n)CH₃, where n is 3 to 17, or 4 to 11,and or 5 to 9. Linear R groups with n of 4 to 11, and or 5 to 9 areadvantageous, and with n of 5 to 9 are particularly advantageous.Optionally, R can contain one methyl or ethyl branch, i.e., R is(CH₂)_(m)[CH(CH₃)](CH₂)_(z)CH₃ or R is (CH₂)[CH(CH₂CH₃)](CH₂)_(y)CH₃,where (m+z) is 1 to 15, advantageously 1 to 9, or 3 to 7, and (x+y) is 1to 14, advantageously 1 to 8, or 2 to 6. Advantageously m>z; m is 0 to15, advantageously 2 to 15, or 3 to 12, more advantageously 4 to 9; andn is 0 to 10, advantageously 1 to 8, or 1 to 6, more advantageously 1 to4. Advantageously x>y; x is 0 to 14, advantageously 1 to 14, or 2 to 11,more advantageously 3 to 8; and y is 0 to 10, advantageously 1 to 8, or1 to 6, more advantageously 1 to 4. Advantageously, the repeat units arearranged in a head-to-tail fashion with minimal head-to-headconnections.

The PAO can be atactic, isotactic, or syndiotactic. In one or moreembodiments, the PAO has essentially the same population of meso andracemic diads, on average, making it atactic. In certain embodiments,the PAO has more than 50%, or more than 60%, or more than 70%, or morethan 80%, advantageously more than 90% meso triads (i.e., [mm]) asdetermined by ¹³C-NMR. In other embodiments, the PAO has more than 50%,or more than 60%, or more than 70%, or more than 80%, advantageouslymore than 90% racemic triads (i.e., [rr]) as determined by ¹³C-NMR. Inother embodiments, the ratio of meso to racemic diads, [m]/[r], asdetermined by ¹³C-NMR is between 0.9 and 1.1. In another embodiment,[m]/[r] is greater than 1.0 and [m]/[r] is less than 1.0 in yet anotherembodiment.

The PAO plasticizer can include one or more distinct PAO components. Inone or more embodiments, the plasticizer is a blend of one or more PAOswith different compositions (e.g., when different alpha-olefin poolswere used in two or more reactor trains of the in-line blendingprocesses disclosed in U.S. Patent Application No. 60/876,193, filed onDec. 20, 2006 to make the oligomers) and/or different physicalproperties (e.g., kinematic viscosity, pour point, and/or viscosityindex).

In one or more embodiments, the PAO or blend of PAOs has anumber-averaged molecular weight (M_(n)) of from 400 to 15,000 g/mol,advantageously 400 to 12,000 g/mol, or 500 to 10,000 g/mol, or 600 to8,000 g/mol, more advantageously 800 to 6,000 g/mol, or 1,000 to 5,000g/mol). In one or more embodiments, the PAO or blend of PAOs has a M_(n)greater than 1,000 g/mol, or greater than 1,500 g/mol, advantageouslygreater than 2,000 g/mol, or greater than 2,500 g/mol).

In one or more embodiments, the PAO or blend of PAOs has a kinematicviscosity at 100° C. (KV100° C.) of 3 cSt or more, or 4 cSt or more, or5 cSt or more, or 6 cSt or more, or 8 cSt or more, or 10 cSt or more, or20 cSt or more, or 30 cSt or more, or 40 cSt or more, advantageously 100or more, or 150 cSt or more. In one or more embodiments, the PAO has aKV100° C. of 3 to 3,000 cSt, or 4 to 1,000 cSt, advantageously 6 to 300cSt, or 8 to 150 cSt, or 8 to 100 cSt, or 8 to 40 cSt). In one or moreembodiments, the PAO or blend of PAOs has a KV100° C. of 10 to 1000 cSt,advantageously 10 to 300 cSt, or 10 to 100 cSt. In yet anotherembodiment, the PAO or blend of PAOs has a KV100° C. of 4 to 8 cSt. Inyet another embodiment, the PAO or blend of PAOs has a KV100° C. of 25to 300 cSt, advantageously 40 to 300 cSt, or 40 to 150 cSt. In one ormore embodiments, the PAO or blend of PAOs has a KV100° C. of 100 to 300cSt.

In one or more embodiments, the PAO or blend of PAOs has a ViscosityIndex (VI) of 120 or more, advantageously 130 or more, or 140 or more,or 150 or more, or 170 or more, or 190 or more, or 200 or more,preferably 250 or more, or 300 or more. In one or more embodiments, thePAO or blend of PAOs has a VI of 120 to 350, advantageously 130 to 250.

In one or more embodiments, the PAO or blend of PAOs has a pour point of−10° C. or less, advantageously −20° C. or less, or −25° C. or less, or−30° C. or less, or −35° C. or less, or −40° C. or less, or −50° C. orless. In one or more embodiments, the PAO or blend of PAOs has a pourpoint of −15 to −70° C., advantageously −25 to −60° C.

In one or more embodiments, the PAO or blend of PAOs has a glasstransition temperature (T_(g)) of −40° C. or less, advantageously −50°C. or less, or −60° C. or less, or −70° C. or less, or −80° C. or less.In one or more embodiments, the PAO or blend of PAOs has a glasstransition temperature (Tg) measured by differential-thermal calorimetryof −50 to −120° C., advantageously −60 to −100° C., or −70 to −90° C.

In one or more embodiments, the PAO or blend of PAOs has a flash pointof 200° C. or more, advantageously 210° C. or more, or 220° C. or more,or 230° C. or more, more advantageously between 240° C. and 290° C.

In one or more embodiments, the PAO or blend of PAOs has a specificgravity (15.6° C.) of 0.86 or less, advantageously 0.855 or less, or0.85 or less, or 0.84 or less.

In one or more embodiments, the PAO or blend of PAOs has a molecularweight distribution as characterized by the ratio of the weight- andnumber-averaged molecular weights (M_(w)/M_(n)) of 2 or more,advantageously 2.5 or more, or 3 or more, or 4 or more, or 5 or more, or6 or more, or 8 or more, or or more. In one or more embodiments, the PAOor blend of PAOs has a M_(w)/M_(n) of 5 or less, advantageously 4 orless, or 3 or less and a KV100° C. of 10 cSt or more, advantageously 20cSt or more, or 40 cSt or more, or 60 cSt or more.

Particularly advantageous PAOs and blends of PAOs are those having a) aflash point of 200° C. or more, advantageously 210° C. or more, or 220°C. or more, or 230° C. or more; and b) a pour point less than −20° C.,advantageously less than −25° C., or less than −30° C., or less than−35° C. or less than −40° C.) and/or a KV100° C. of 10 cSt or more,advantageously 35 cSt or more, or 40 cSt or more, or 60 cSt or more.

Further advantageous PAOs or blends of PAOs have a KV100° C. of at least3 cSt, advantageously at least 4 cSt, or at least 6 cSt, or at least 8cSt, or at least 10 cSt; a VI of at least 120, advantageously at least130, or at least 140, or at least 150; a pour point of −10° C. or less,advantageously −20° C. or less, or −30° C. or less, or −40° C. or less;and a specific gravity (15.6° C.) of 0.86 or less advantageously 0.855or less, or 0.85 or less, or 0.84 or less.

Advantageous blends of PAOs include blends of two or more PAOs where theratio of the highest KV100° C. to the lowest KV100° C. is at least 1.5,advantageously at least 2, or at least 3, or at least 5. In anadditional embodiment, KV100° C. of the PAOs are less than 1000 cSt,advantageously less than 300 cSt, or less than 150 cSt, or less than 100cSt, or less than 40 cSt, or less than 25 cSt, or less than 10 cSt, orless than 8 cSt.

Advantageous blends of PAO also include: blends of two or more PAOswhere at least one PAO has a KV100° C. of 300 cSt or more and at leastone PAO has a KV100° C. of less than 300 cSt, advantageously 150 cSt orless, or 100 cSt or less, or 40 cSt or less; blends of two or more PAOswhere at least one PAO has a KV100° C. of 150 cSt or more and at leastone PAO has a KV100° C. of less than 150 cSt, advantageously 100 cSt orless, or 40 cSt or less); blends of two or more PAOs where at least onePAO has a KV100° C. of 100 cSt or more and at least one PAO has a KV100°C. of less than 100 cSt, advantageously 40 cSt or less, or 25 cSt orless, or 10 cSt or less; blends of two or more PAOs where at least onePAO has a KV100° C. of 40 cSt or more and at least one PAO has a KV100°C. of less than 40 cSt, advantageously 25 cSt or less, or 10 cSt orless, or 8 cSt or less; blends of two or more PAOs where at least onePAO has a KV100° C. of 10 cSt or more and at least one PAO has a KV100°C. of less than 10 cSt, advantageously 8 cSt or less, or 6 cSt or less,or 4 cSt or less); blends of two or more PAOs where at least one PAO hasa KV100° C. of 8 cSt or more and at least one PAO has a KV100° C. ofless than 8 cSt, advantageously 6 cSt or less, or 4 cSt or less); andblends of two or more PAOs where at least one PAO has a KV100° C. of 6cSt or more and at least one PAO has a KV100° C. of less than 6 cSt,advantageously 4 cSt or less).

Examples for PAO plasticizer components with desirable propertiesinclude commercial products, such as SpectraSyn™ and SpectraSyn Ultra™from ExxonMobil Chemical (USA), some of which are summarized in Table A.Other useful PAOs include those available as Synfluid™ fromChevronPhillips Chemical (USA), as Durasyn™ from Ineos (UK), as Nexbase™from Neste Oil (Finland), and as Synton™ from Chemtura (USA).

Commercial Examples of PAOs KV KV Pour Flash 40° C., 100° C., Point,Specific Point, cSt cSt VI ° C. gravity ° C. SpectraSyn 4 19 4 126 −660.820 220 SpectraSyn Plus 4 17 4 126 −60 0.820 228 SpectraSyn 6 31 6 138−57 0.827 246 SpectraSyn Plus 6 30 6 143 −54 0.827 246 SpectraSyn 8 48 8139 −48 0.833 260 SpectraSyn 10 66 10 137 −48 0.835 266 SpectraSyn 40396 39 147 −36 0.850 281 SpectraSyn 100 1240 100 170 −30 0.853 283SpectraSyn Ultra 1,500 150 218 −33 0.850 >265 150 SpectraSyn Ultra 3,100300 241 −27 0.852 >265 300 SpectraSyn Ultra 10,000 1,000 307 −180.855 >265 1000

The disclosed novel processes for making in-line plasticized polymerscan make polymer blends with many different in-line produced and blendedplasticizer components. These plasticizer components are made in one ormore parallel reactor trains of the in-line polymer blending processdisclosed in U.S. Patent Application No. 60/876,193 filed on Dec. 20,2006. Some embodiments for making in-line plasticized polymers can makepolymer blends comprising PAO plasticizer components.

II. Off-Line-Produced In-Line-Blended Plasticizers

The plasticizer component may comprise, or may consist essentially ofone or more fluids and/or polymers that are produced off-line, but arein-line blended from one or more polymer/additive storage tanks with theplasticized polymer blend components of the in-line blending processdisclosed herein. Suitable off-line-produced plasticizers are capable ofbeing codissolved with the base polymer in the high-pressure separatorand have a glass transition temperature (Tg) of −20 or less and at leastone of the following: a Mw of 10 kg/mol or less, or a flexural modulusof 20 MPa or less. Non-limiting exemplary plasticizers conducive toin-line blending include paraffin oils and waxes (e.g., isoparaffins orn-paraffins), mineral oils, vegetable or other bio-derived oils, andother synthetic or natural oils such as described in SYNTHETICS, MINERALOILS, AND BIO-BASED LUBRICANTS: CHEMISTRY AND TECHNOLOGY, L. S. Rudnick,Ed., CRC Press, 2006. Particularly preferred plasticizers includeisoparaffins, process oils, high purity hydrocarbon fluids derived froma so-called Gas-To-Liquids processes, and Group III lubricantbasestocks.

II.A. Off-Line-Produced In-Line-Blended Paraffins

The off-line produced plasticizer may comprise, or may consistessentially of one or more C₆ to C₂₀₀ paraffins. In one embodiment, theparaffin plasticizer may comprise C₆ to C₁₀₀ paraffins, or C₆ to C₂₀₀paraffins, or C₈ to C₁₀₀ paraffins. In yet another embodiment, theparaffin plasticizer may comprise C₂₀ to C₁₅₀₀ paraffins, or C₂₀ to C₅₀₀paraffins, or C₃₀ to C₄₀₀ paraffins, or C₄₀ to C₂₅₀ paraffins.

In another embodiment, an paraffin plasticizer may comprise, or mayconsist essentially of one or more linear or normal paraffins(n-paraffins). Advantageous paraffin plasticizers comprise at least 50weight %, or at least 60 wt %, or at least 70 wt %, or at least 80 wt %,or at least 90 wt %, or at least 95 wt % or essentially 100 wt % of C₅to C₂₅ n-paraffins, or C₅ to C₂₀ n-paraffins, or C₅ to C₁₅ n-paraffins.Advantageous n-paraffins may also comprise less than 0.1 wt %, or lessthan 0.01 wt % aromatics.

In another embodiment, an paraffin plasticizer may comprise, or mayconsist essentially of one or more branched paraffins (isoparaffins).Advantageous paraffin plasticizers comprise at least 50 wt %, or atleast 60 wt at least 70 wt %, or at least 80 wt %, or at least 90 wt %,or at least 95 wt % or essentially 100 wt % of C₆ to C₁₅₀ isoparaffins.The paraffin plasticizer may also comprise C₆ to C₁₀₀ isoparaffins, orC₆ to C₂₅ isoparaffins, or C₈ to C₂₀ isoparaffins. Advantageousisoparaffins may have: a density of 0.70 to 0.83 g/mL; and/or a pourpoint of −40° C. or less, or −50° C. or less; and/or a viscosity at 25°C. of 0.5 to 20 cSt; and/or a weight-averaged molecular weight (Mw) of100 to 300 g/mol.

The isoparaffins may include greater than 50 wt % (by total weight ofthe isoparaffin) mono-methyl species, for example, 2-methyl, 3-methyl,4-ethyl, 5-methyl or the like, with minimum formation of branches withsubstituent groups of carbon number greater than 1, (e.g., ethyl,propyl, butyl and the like). In one embodiment, the isoparaffin includesgreater than 70 wt % mono-methyl species, based on the total weight ofthe isoparaffin present. Advantageously, the isoparaffin has a boilingpoint of from 100° C. to 350° C., or 110° C. to 320° C. In preparingdifferent grades of isoparaffin, a paraffinic mixture may befractionated into cuts having narrow boiling ranges, for example, ofabout 35° C.

Suitable isoparaffins are commercially available under the tradenameISOPAR (ExxonMobil Chemical Company, Houston Tex.), and are describedin, for example, U.S. Pat. No. 6,197,285 (column 5, lines 1-18), U.S.Pat. Nos. 3,818,105 and 3,439,088, and sold commercially as ISOPARseries of isoparaffins, examples of which are summarized in the tablebelow.

Commercial Examples of Isoparaffins Distillation Pour Avg. Saturates &range point Specific KV 25° C. aromatics Name (° C.) (° C.) Gravity(cSt) (wt %) ISOPAR E 117-136 −63 0.72 0.85 <0.01 ISOPAR G 161-176 −570.75 1.46 <0.01 ISOPAR H 178-188 −63 0.76 1.8 <0.01 ISOPAR K 179-196 −600.76 1.85 <0.01 ISOPAR L 188-207 −57 0.77 1.99 <0.01 ISOPAR M 223-254−57 0.79 3.8 <0.01 ISOPAR V 272-311 −63 0.82 14.8 <0.01

II.B. Off-Line-Produced In-Line-Blended Mineral and Process Oils

The off-line produced plasticizer may comprise, or may consistessentially of one or more mineral oils (also called process oils).

Characteristics of some commercially available mineral oils used asprocess oils are listed in the table below. Such fluids typically have aviscosity index less than 110, and many have a viscosity index of 100 orless. Advantageously, the mineral oil plasticizer has a kinematicviscosity at 40° C. of 80 cSt or more and a pour point of −15° C.

Commercial Examples of Process Oils KV @ KV @ Pour Flash 40° C. 100° C.Point Specific Point cSt cSt VI ° C. gravity ° C. Drakeol 34¹ 76 9 99−12 0.872 254 Paralux 1001R² 20 4 99 −17 0.849 212 Paralux 2401R² 43 6101 −12 0.866 234 Paralux 6001R² 118 12 102 −21 0.875 274 Sunpar 120³ 416 106 −15 0.872 228 Sunpar 150³ 94 11 97 −12 0.881 245 Sunpar 2280³ 47531 95 −9 0.899 305 Plastol 135⁴ 24 5 104 −9 0.865 210 Plastol 537⁴ 10311 97 −3 0.880 240 Plastol 2105⁴ 380 30 110 −15 0.885 270 Flexon 843⁴ 305 91 −12 0.869 218 Flexon 865⁴ 106 11 93 −3 0.879 252 Flexon 815⁴ 457 32101 −9 0.895 310 Shellflex 210⁵ 19 4 95 −18 0.860 216 Shellflex 330⁵ 709 95 −10 0.875 256 Shellflex 810⁵ 501 33 95 −9 0.896 324 Diana PW32⁶ 315 104 −18 0.862 226 Diana PW90⁶ 90 11 105 −22 0.872 262 Diana PW380⁶ 37626 106 −19 0.877 293 ¹Available from Penreco (USA). ²Available fromChevron (USA). ³Available from Sunoco (USA). ⁴Available from ExxonMobil(USA). ⁵Available from Royal Dutch Shell (UK/Netherlands). ⁶Availablefrom Idemitsu (Japan).

In certain embodiments, the mineral oil plasticizer has a viscosityindex less than 120 (preferably 90 to 119); and a kinematic viscosity at40° C. of 80 cSt or more (preferably 90 cSt or more, or 100 cSt or more,or 120 cSt or more, or 150 cSt or more, or 200 cSt or more, or 250 cStor more, or 300 cSt or more); and a pour point of 15° C. or less(preferably 18° C. or less, or 20° C. or less, or 25° C. or less, or 30°C. or less, or 35° C. or less).

In other embodiments, the mineral oil plasticizer comprises one or moreGroup I or II lubricant basestocks. Group I basestocks are mineral oilsthat may have been refined using solvent extraction of aromatics,solvent dewaxing, and hydrofining; they may have sulfur levels greaterthan 0.03 weight %, saturates levels of 60 to 80%, and a VI of about 90.Group II basestocks are mineral oils that have been mildly hydrocrackedwith conventional solvent extraction of aromatics, solvent dewaxing, andmore severe hydrofining to reduce sulfur levels to less than or equal to0.03 weight %, as well as removing double bonds from some of theolefinic and aromatic compounds such that saturate levels are greaterthan 95-98%; they have a VI of about 80-120.

II.C. Off-Line-Produced In-Line-Blended High-Purity Hydrocarbon Fluids

The off-line produced plasticizer may comprise, or may consistessentially of one or more “high purity” hydrocarbon fluids.

In one embodiment, the “high purity” hydrocarbon fluids comprise one ormore paraffins having 6 to 1500 carbon atoms, or 8 to 1000 carbon atoms,or 10 to 500 carbon atoms, or 12 to about 200 carbon atoms, or 14 to 150carbon atoms, or 16 to 100 carbon atoms, or 20 to 500 carbon atoms, or30 to 400 carbon atoms, or 40 to 200 carbon atoms, or 20 to 100 carbonatoms. The high purity hydrocarbon fluid composition may have anisoparaffin:n-paraffin ratio of about 0.5:1 to about 9:1, or about 1:1to about 4:1. The isoparaffins of the “high purity” hydrocarbon fluidcomposition may contain greater than fifty percent mono-methyl species,e.g., 2-methyl, 3-methyl, 4-methyl, ≧5-methyl or the like, with minimumformation of branches with substituent groups of carbon number greaterthan one, i.e., ethyl, propyl, butyl or the like, based on the totalweight of isoparaffins in the mixture. Advantageously, the isoparaffinsof the “high purity” hydrocarbon fluid composition contain greater than70 percent of the mono-methyl species, based on the total weight of thecomposition.

An advantageous high purity hydrocarbon fluid may have: a KV at 25° C.of 1 to 100,000 cSt, or 10 cSt to 2000 cSt; and/or a KV at 40° C. of 1to 30,000 cSt, or 10 cSt to 2000 cSt; and/or a pour point below −10° C.,or below −20° C., or below −30° C., or from about −20° C. to about −70°C. In an advantageous embodiment, a high purity hydrocarbon fluid maycomprise paraffins having: a number average molecular weight of 500 to21,000 g/mol; and/or less than 10% side chains having 4 or more carbons,or less than 8 weight %, or less than 5 weight %, or less than 3 weight%, or less than 2 weight %, or less than 1 weight %, or less than 0.5weight %, or less than 0.1 weight %, or at less than 0.1 weight %, or at0.001 weight %; and/or at least 1 or 2 carbon branches present at 15weight % or more, or 20 weight % or more, or 25 weight % or more, or 30weight % or more, or 35 weight % or more, or 40 weight % or more, or 45weight % or more, or 50 weight % or more; and/or less than 2.5 weight %cyclic paraffins, or less than 2 weight %, or less than 1 weight %, orless than 0.5 weight %, or less than 0.1 weight %, or at less than 0.1weight %, or at 0.001 weight %.

In another advantageous embodiment, a high purity hydrocarbon fluid maycomprise paraffins having: a KV of 2 cSt or more at 100° C.; and/or aviscosity index of 120 or more, or 130 or more, or 140 or more, or 150or more, or 170 or more, or 190 or more, or 200 or more, or 250 or more,or 300 or more; and/or a mixture of paraffins of carbon number rangingfrom about C₈ to C₂₀, or from about C₈ to C₅₀₀; and/or a molar ratio ofisoparaffins to n-paraffins of about 0.5:1 to about 9:1; and/or greaterthan 50 percent of mono-methyl species, based on the total weight of theisoparaffins; and/or a pour point of about −20° F. to about −70° F., or−10 to −70° C.; and/or a kinematic viscosity at 25° C. of about 1 cSt toabout 10 cSt; and/or a kinematic viscosity at 100° C. of about 3 toabout 25 cSt; and/or a carbon number of C₁₀ to about C₁₆, or of aboutC₂₀ to about C₁₀₀; and/or greater than 70 percent mono-methyl species;and/or a boiling temperature of about 320° F. to about 650° F., or ofabout 350° F. to about 550° F.

In an advantageous embodiment, the high-purity hydrocarbon fluidcomprises a mixture of paraffins having a carbon number of C₁₀ to aboutC₁₆, or of about C₂₀ to about C₁₀₀; contains greater than 70 percentmono-methyl species; has a boiling temperature of about 350° F. to about550° F., and has a molar ratio of isoparaffins to n-paraffins of about1:1 to about 4:1. The high purity hydrocarbon fluid may also be derivedfrom a Fischer-Tropsch process followed by a wax isomerization process,such as those disclosed in U.S. Pat. No. 5,906,727.

In another embodiment, the off-line plasticizer is a high-purityhydrocarbon fluid of lubricating viscosity comprising a mixture of C₂₀to C₁₂₀ paraffins, 50 wt % or more being isoparaffinic hydrocarbons andless than 50 wt % being hydrocarbons that contain naphthenic and/oraromatic structures. Or, the mixture of paraffins comprises a waxisomerate lubricant base stock or oil, which includes:

1. hydroisomerized natural and refined waxes, such as slack waxes,deoiled waxes, normal alpha-olefin waxes, microcrystalline waxes, andwaxy stocks derived from gas oils, fuels hydrocracker bottoms,hydrocarbon raffinates, hydrocracked hydrocarbons, lubricating oils,mineral oils, polyalphaolefins, or other linear or branched hydrocarboncompounds with carbon number of about 20 or more; and2. hydroisomerized synthetic waxes, such as Fischer-Tropsch waxes (i.e.,the high boiling point residues of Fischer-Tropsch synthesis, includingwaxy hydrocarbons); or mixtures thereof.

Particularly advantageous are lubricant base stocks or oils derived fromhydrocarbons synthesized in a Fischer-Tropsch process as part of anoverall Gas-to-Liquids (GTL) process.

In one embodiment, the mixture of paraffins useful as an off-lineplasticizer has:

1. a naphthenic content of less than 40 wt %, or less than 30 wt %, orless than 20 wt %, or less than 15 wt %, or less than 10 wt %, or lessthan 5 wt %, or less than 2 wt %, or less than 1 wt % (based on thetotal weight of the hydrocarbon mixture); and/or2. a normal paraffins content of less than 5 wt %, or less than 4 wt %,or less than 3 wt %, or less than 1 wt % (based on the total weight ofthe hydrocarbon mixture); and/or3. an aromatic content of 1 wt % or less, or 0.5 wt % or less; and/or4. a saturates level of 90 wt % or higher, or 95 wt % or higher, or 98wt % or higher, or 99 wt % or higher; and/or5. a branched paraffin:normal paraffin ratio greater than about 10:1, orgreater than 20:1, or greater than 50:1, or greater than 100:1, orgreater than 500:1, or greater than 1000:1; and/or6. sidechains with 4 or more carbons making up less than 10% of allsidechains, or less than 5%, or less than 1%; and/or7. sidechains with 1 or 2 carbons making up at least 50% of allsidechains, or at least 60%, or at least 70%, or at least 80%, or atleast 90%, or at least 95%, or at least 98%; and/or8. a sulfur content of 300 ppm or less, or 100 ppm or less, or 50 ppm orless, or ppm or less (where ppm is on a weight basis.

In another embodiment, the mixture of paraffins useful as an off-lineplasticizer has:

1. a number-averaged molecular weight of 300 to 1800 g/mol, or 400 to1500 g/mol, or 500 to 1200 g/mol, or 600 to 900 g/mol; and/or2. a kinematic viscosity at 40° C. of 10 cSt or more, or 25 cSt or more,or between about 50 and 400 cSt; and/or3. a kinematic viscosity at 100° C. ranging from 2 to 50 cSt, or 3 to 30cSt, or 5 to 25 cSt, or 6 to 20 cSt, more or 8 to 16 cSt; and/or4. a viscosity index (VI) of 80 or greater, or 100 or greater, or 120 orgreater, or 130 or greater, or 140 or greater, or 150 or greater, or 160or greater, or 180 or greater; and/or5. a pour point of −5° C. or lower, or −10° C. or lower, or −15° C. orlower, or −20° C. or lower, or −25° C. or lower, or −30° C. or lower;and/or6. a flash point of 200° C. or more, or 220° C. or more, or 240° C. ormore, or 260° C. or more; and/or7. a specific gravity (15.6° C./15.6° C.) of 0.86 or less, or 0.85 orless, or 0.84 or less.

In an advantageous embodiment, the off-line plastizier is a mixture ofparaffins comprising a GTL base stock or oil. GTL base stocks and oilsare fluids of lubricating viscosity that are generally derived from waxysynthesized hydrocarbons, that are themselves derived via one or moresynthesis, combination, transformation, and/or rearrangement processesfrom gaseous carbon-containing compounds and hydrogen-containingcompounds as feedstocks. Advantageously, the feedstock is “syngas”(synthesis gas, essentially CO and H₂) derived from a suitable source,such as natural gas and/or coal. GTL base stocks and oils include waxisomerates, comprising, for example, hydroisomerized synthesized waxes,hydroisomerized Fischer-Tropsch (F-T) waxes (including waxy hydrocarbonsand possible analogous oxygenates), or mixtures thereof. GTL base stocksand oils may further comprise other hydroisomerized base stocks and baseoils. Particularly advantageous GTL base stocks or oils are thosecomprising mostly hydroisomerized F-T waxes and/or other liquidhydrocarbons obtained by a F-T synthesis process. The production of lubebase stocks by GTL is well known in the art. The in-line blendingprocesses disclosed herein may use off-line-produced GTL base stocksfrom any one of the known GTL processes. Desirable GTL-derived fluidsare expected to become broadly available from several commercialsources, including Chevron, ConocoPhillips, ExxonMobil, Sasol,SasolChevron, Shell, Statoil, and Syntroleum.

II.D. Off-Line-Produced In-Line-Blended Group III Lubricant Basestocks

The off-line produced plasticizer may comprise, or may consistessentially of one or more Group III lubricant basestock, which alsoherein includes mineral oils with a VI of 120 or more (a “Group IIImineral oil”).

In one embodiment, the Group III mineral oil plasticizer has a saturateslevels of 90% or more, or 92% or more, or 94% or more, or 95% or more,or 98% or more; a sulfur content of less than 0.03%, or between 0.001and 0.01%; and a VI of 120 or more, or 130 or more, or 140 or more. Inanother embodiment, the Group III mineral oil plasticizer has akinematic viscosity at 100° C. of 3 to 50, or 4 to 40 cSt, or 6 to 30cSt, or 8 to 20; and/or a Mn of 300 to 5,000 g/mol, or 400 to 2,000g/mol, or 500 to 1,000 g/mol. In another embodiment, the Group IIImineral oil plasticizer has a pour point of −10° C. or less, a flashpoint of 200° C. or more, and a specific gravity (15.6° C.) of 0.86 orless.

Desirable Group III basestocks are commercially available from a numberof sources and include those described in the table below.

Commercial Examples of Group III Basestocks KV @ Pour Flash 100° C.,Point, Specific Point, cSt VI ° C. gravity ° C. UCBO 4R¹ 4.1 127 −180.826 216 UCBO 7R¹ 7.0 135 −18 0.839 250 Nexbase 3043² 4.3 124 −18 0.831224 Nexbase 3050² 5.1 126 −15 0.835 240 Nexbase 3060² 6.0 128 −15 0.838240 Nexbase 3080² 8.0 128 −15 0.843 260 Yubase YU-4³ 4.2 122 −15 0.843230 Yubase YU-6³ 6.5 131 −15 0.842 240 Yubase YU-8³ 7.6 128 −12 0.850260 Ultra-S 4⁴ 4.3 123 −20 0.836 220 Ultra-S 6⁴ 5.6 128 −20 0.839 234Ultra-S 8⁴ 7.2 127 −15 0.847 256 VHVI 4⁵ 4.6 128 −21 0.826 VHVI 8⁵ 8.0127 −12 0.850 248 Visom 4⁶ 4.0 210 Visom 6⁶ 6.6 148 −18 0.836 250¹Available from ChevronTexaco (USA). ²Available from Neste Oil(Finland). ³Available from SK Corp (South Korea). ⁴Available fromConocoPhillips (USA)/S-Oil (South Korea). ⁵Available from PetroCanada(Canada). ⁶Available from ExxonMobil (USA).

II.E. Other Off-Line-Produced In-Line-Blended Plasticizers

The off-line produced in-line-blended plasticizers may also include anyother compounds used for plasticizing polymers. These include phthalateesters, such as di-isononyl phthalate (DINP), di-isoctyl phthalate(DOP), trimellitites, citrates, etc. Examples for polymeric plasticizerscan be found in J. K. Sears, J. R. Darby, THE TECHNOLOGY OFPLASTICIZERS, Wiley, New York, 1982.

III. Advantageous Properties for Liquid Plasticizers

Certain embodiments will use plasticizers that are liquids at ambienttemperature. The advantageous properties for such liquid plasticizerscan be defined as follows.

In an advantageous embodiment, any of the plasticizers described abovehas a flash point of 200° C. or more (or 220° C., or more, or 230° C. ormore, or 250° C. or more). In a particularly advantageous embodiment anyof the plasticizers described above has a flash point of 200° C. or more(or 220° C., or more, or 230° C. or more, or 250° C. or more) and a pourpoint of −20° C. or less (or less than −25° C., or less than −30° C., orless than −35° C., or less than −40° C.), and/or a kinematic viscosityat 100° C. of 35 cSt or more (or 40 cSt or more, or 50 cSt or more, or60 cSt or more).

In another advantageous embodiment, any of the plasticizers describedabove has flash point of 200° C. or greater, or 220° C. or greater, or200 to 350° C., or 210 to 300° C., or 215 to 290° C., or 220 to 280° C.,or 240 to 280° C., wherein a desirable range may be any combination ofany lower limit with any upper limit described herein.

In still another advantageous embodiment, any of the plasticizersdescribed above has a pour point of −10° C. or less, or −20° C. or less,or −30° C. or less, or −40° C. or less, or −45° C. or less, or −50° C.or less, or −10 to −80° C., or −15 to −75° C. or −0 to −70° C., or −25to −65° C., wherein a desirable range may be any combination of anylower limit with any upper limit described herein.

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a viscosity index (VI) of 100 or more, or 110 ormore, or 120 or more, or 120 to 350, or 135 to 300, or 140 to 250, or150 to 200, wherein a desirable range may be any combination of anylower limit with any upper limit described herein.

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a specific gravity of 0.86 or less, or 0.855 orless, or 0.84 or less, or 0.78 to 0.86, or 0.80 to 0.85, or 0.82 to0.845, wherein a desirable range may be any combination of any lowerlimit with any upper limit described herein.

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a kinematic viscosity at 100° C. (KV100° C.) of 4cSt or more, or 5 cSt or more, or 6 to 5000 cSt, or 8 to 3000 cSt, or 10to 1000 cSt, or 12 to 500 cSt, or 15 to 350 cSt, or 35 cSt or more, or40 cSt or more, wherein a desirable range may be any combination of anylower limit with any upper limit described herein.

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a number-averaged molecular weight (Mn) of 300 g/molor more, or 500 g/mol or more, or 300 to 21,000 g/mol, or 300 to 10,000g/mol, or 400 to 5,000 g/mol, or 500 to 3,000 g/mol, or less than 1,000g/mol, wherein a desirable range may be any combination of any lowerlimit with any upper limit described herein.

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a specific gravity of 0.86 or less (or 0.855 orless, or 0.85 or less), and one or more of the following:

a) a VI of 120 or more (or 135 or more, or 140 or more), and/orb) a flash point of 200° C. or more (or 220° C. or more, or 240° C. ormore).

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a pour point of −10° C. or less (or −15° C. or less,or −20° C. or less, or −25° C. or less), a VI of 120 or more (or 135 ormore, or 140 or more), and optionally a flash point of 200° C. or more(or 220° C. or more, or 240° C. or more).

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a pour point of −20° C. or less (or −25° C. or less,or −30° C. or less, or −40° C. or less) and one or more of thefollowing:

a) a flash point of 200° C. or more (or 220° C. or more, or 240° C. ormore), and/orb) a VI of 120 or more (or 135 or more, or 140 or more), and/orc) a KV100° C. of 4 cSt or more (or 6 cSt or more, or 8 cSt or more, or10 cSt or more), and/ord) a specific gravity of 0.86 or less (or 0.855 or less, or 0.85 orless).

In another advantageous embodiment, any of the plasticizers describedabove has a KV100° C. of 4 cSt or more (or 5 cSt or more, or 6 cSt ormore, or 8 cSt or more, or 10 cSt or more), a specific gravity of 0.86or less (or 0.855 or less, or 0.85 cSt or less), and a flash point of200° C. or more (or 220° C. or more, or 240° C. or more).

In yet another advantageous embodiment, any of the plasticizersdescribed above has a flash point of 200° C. or more (or 220° C. ormore, or 240° C. or more), a pour point of 110° C. or less (or 15° C. orless, or 20° C. or less, or 25° C. or less), a specific gravity of 0.86or less (or 0.855 or less, or 0.85 or less), a KV100° C. of 4 cSt ormore (or 5 cSt or more, or 6 cSt or more, or 8 cSt or more, or 10 cSt ormore), and optionally a VI of 100 or more (or 120 or more, or 135 ormore).

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a KV100° C. of 35 cSt or more (or 40 or more) and aspecific gravity of 0.86 or less (or 0.855 or less), and optionally oneor more of the following:

a) a flash point of 200° C. or more (or 220° C. or more, or 240° C. ormore), and/or b) a pour point of 10° C. or less (or 15° C. or less, or20° C. or less, or 25° C. or less).

In yet another advantageous embodiment, any of the plasticizersdescribed above has a flash point of 200° C. or more (or 210° C. ormore, or 220° C. or more), a pour point of 10° C. or less (or 20° C. orless, or 30° C. or less), and a KV100° C. of 6 cSt or more (or 8 cSt ormore, or 10 cSt or more, or 15 cSt or more).

In still yet another advantageous embodiment, any of the plasticizersdescribed above has a pour point of 40° C. or less (or 50° C. or less)and a specific gravity of 0.84 or less (or 0.83 or less).

It should be understood that sometimes even soft polyolefins needplasticizer to further soften them while the same soft polyolefins mayserve as plasticizers, particularly with highly crystalline, hardpolyolefins, such as, for example, ethylene and propylene homopolymers.Therefore, such soft polyolefins may serve both as plasticizers and basepolymers. The description of such dual-purpose soft polyolefin (SPO)polymers is given below.

IV. Soft Polyolefin (SPO) Polymers

Preferred SPOs have a percent crystallinity of 0.1% to less than 35%.Advantageously, within this range, the SPO comprises less than 30%crystallinity, or less than 25% crystallinity, or less than 20%crystallinity, or less than 15% crystallinity, or less than 10%crystallinity. Also advantageously, the SPO comprises at least 0.5%crystallinity, or at least 1% crystallinity, or at least 2%crystallinity, or at least 5% crystallinity.

Advantageously, SPOs have a DSC melting point of 105° C. or less, or 90°C. or less, or between 25 and 90° C., or between 30 and 80° C., orbetween 35 and 75° C., as measured by DSC and have a Mw/Mn ratio of lessthan 5, or between 1.5 and 4, or between 1.5 and 3.

In one embodiment, a useful SPO comprises a first monomer consisting ofat least 50 wt % ethylene or at least 50 wt % propylene, and less than50 wt % of at least one other monomer selected from C₂-C₂₀ olefins, orC₂-C₆ alpha-olefins, which is different from the first monomer. Suitableolefin comonomers may be any polymerizable olefin monomer and arepreferably a linear, branched or cyclic olefin, even more preferably analpha-olefin. Examples of suitable olefins include butene, isobutylene,pentene, isopentene, cyclopentene, hexene, isohexene, cyclohexene,heptene, isoheptene, cycloheptene, octene, isooctene, cyclooctene,nonene, cyclononene, decene, isodecene, dodecene, isodecene,4-methyl-pentene-1,3-methyl-pentene-1,3,5,5-trimethyl hexene-1. Suitablecomonomers also include dienes, trienes, and styrenic monomers such asstyrene, alpha-methyl styrene, para-alkyl styrene (such as para-methylstyrene), hexadiene, norbornene, vinyl norbornene, ethylidenenorbornene, butadiene, isoprene, heptadiene, octadiene, andcyclopentadiene.

IV.A. Propylene-Rich Soft Polyolefins

A propylene-rich soft polyolefin (prSPO) is a propylene copolymer or apropylene homopolymer with a low level of isotactic or syndiotacticmonomer orientation in the polymer chain comprising at least 50 wt %propylene and having the properties of a soft polyolefin. In someembodiments, the prSPO comprises at least 60 wt % propylene, or at least70 wt % propylene, or at least 80 wt % propylene, or at least 90 wt %propylene, or 100 wt % propylene.

In one embodiment, the prSPO has a mm triad tacticity index of 75% ormore (or 80% or more, or 85% or more, or 90% or more). In anotherembodiment, the prSPO has a melt flow rate (MFR) of 0.1 to 2000 dg/10min (preferably 100 dg/10 min or less). In another embodiment, the prSPOhas an intermolecular compositional distribution as determined bythermal fractionation in hexane such that 85% by weight or more of thepolyolefin is isolated as one or two adjacent, soluble fractions withthe balance of the polyolefin in immediately preceding or succeedingfractions; and wherein each of these fractions has a wt % comonomercontent with a difference of no greater than 20 wt % relative to theaverage wt % co-monomer content of the copolymer polyolefin. In anotherembodiment, the prSPO has an Mw/Mn of 1.5 to 40, preferably 1.6 to 20,preferably 1.8 to 10, even more preferably 1.8 to 2.5.

In one embodiment, a prSPO has a heat of fusion of less than 70 J/g anda mm triad tacticity index of 75% or more; and/or a MFR of 0.1 to 2000dg/min (preferably 100 dg/min or less); and/or an intermolecularcompositional distribution as determined by thermal fractionation inhexane such that 85% by weight or more of the polymer is isolated as oneor two adjacent, soluble fractions with the balance of the polymer inimmediately preceding or succeeding fractions; and wherein each of thesefractions has a wt % comonomer content with a difference of no greaterthan 20 wt % relative to the average wt % comonomer content of thecopolymer; and/or an Mw/Mn of 1.5 to 4.

Advantageous prSPOs useful in this invention preferably have a Melt FlowRate (MFR) of 0.1 to 200 g/10 min, preferably 0.1 to 100, preferably 0.5to 50, preferably 1 to 25, preferably 1 to 15, preferably 2 to 10 g/10min; alternately the MFR is from 15 to 50 g/10 min.

Advantageous prSPOs useful in the processes of this disclosure have anintermolecular composition distribution of 75% or more, preferably 80%or more, preferably 85% or more, preferably 90% or more by weight of thepolymer isolated as one or two adjacent, soluble fractions with thebalance of the polymer in immediately preceding or succeeding fractions;and wherein each of these fractions has a weight % comonomer contentwith a difference of no greater than 20 wt % (relative), preferably 10%(relative), of the average weight % comonomer of the copolymer. Thefractions are obtained at temperature increases of approximately 8° C.between stages.

The intermolecular composition distribution of the prSPO may bedetermined by thermal fractionation in hexane as follows: about 30 gramsof the prSPO is cut into small cubes of about ⅛ inch (0.32 cm) on theside and is then introduced into a thick walled glass bottle closed withscrew cap along with 50 mg of Irganox1076, an antioxidant commerciallyavailable from Ciba-Geigy Corporation. Then, 425 mL of hexane (aprincipal mixture of normal and iso-isomers) is added to the contents ofthe bottle and the sealed bottle is maintained at about 23° C. for 24hours. At the end of this period, the solution is decanted and theresidue is treated with additional hexane for an additional 24 hours at23° C. At the end of this period, the two hexane solutions are combinedand evaporated to yield a residue of the polymer soluble at 23° C. Tothe residue is added sufficient hexane to bring the volume to 425 mL andthe bottle is maintained at about 31° C. for 24 hours in a coveredcirculating water bath. The soluble polymer is decanted and theadditional amount of hexane is added for another 24 hours at about 31°C. prior to decanting. In this manner, fractions of the prSPO soluble at40° C., 48° C., 55° C., and 62° C. are obtained at temperature increasesof approximately 8° C. between stages. The soluble polymers are dried,weighed and analyzed for composition, as wt % ethylene content. Toproduce a prSPO copolymer having the desired narrow composition, it isbeneficial if (1) a single sited metallocene catalyst is used whichallows only a single statistical mode of addition of the first andsecond monomer sequences and (2) the copolymer is well-mixed in acontinuous flow stirred tank polymerization reactor which allows only asingle polymerization environment for substantially all of the polymerchains of the copolymer.

In some advantageous embodiments, the prSPO may comprise apropylene-based copolymer referred to herein as a random copolymer ofpropylene or as a propylene-“comonomer” plastomer (e.g.,propylene-ethylene plastomer). Suitable random copolymers of propylenehave a heat of fusion of less than 70 J/g, and thus are lowcrystallinity, and advantageously comprise an average propylene contenton a molar basis of from about 68 mol % to about 92 mol %, or from about75 mol % to about 91 mol %, or from about 78 mol % to about 88 mol %, orfrom about 80 mol % to about 88 mol %. The balance of the randomcopolymer of propylene (i.e., the one or more comonomers) may be one ormore alpha-olefins as specified above and/or one or more diene monomers.Advantageously, the balance of the random copolymer of propylene isethylene.

The comonomer of the random copolymer of propylene may comprise about 8to 32 mol % of ethylene (C₂) and/or a C₄-C₂₀ olefin, advantageouslyabout 9 to about 25 mol %, or about 12 to about 22 mol %, or about 13 to20 mol % being.

Advantageously, the random copolymer of propylene comprises about 8 to32 mol % ethylene, more preferably about 9 to about 25 mol % ethylene,even more preferably about 12 to about 22 mol % ethylene, with about 13to 20 mol % ethylene being still more preferred as the comonomer.

The random copolymer of propylene may have a weight-averaged molecularweight (Mw) of 5,000,000 g/mol or less, a number-averaged molecularweight (Mn) of about 3,000,000 g/mol or less, a z-average molecularweight (Mz) of about 5,000,000 g/mol or less, and a g′ index of 1.5 orless measured at the weight-averaged molecular weight (Mw) of thepolymer using isotactic polypropylene as the baseline, all of which maybe determined by GPC, also known as size exclusion chromatography, e.g.,3D SEC.

In an embodiment, the random copolymer of propylene may have a Mw ofabout 5,000 to about 5,000,000 g/mole, more preferably a Mw of about10,000 to about 1,000,000 g/mol, more preferably a Mw of about 20,000 toabout 500,000, more preferably a Mw of about 50,000 to about 300,000g/mol, wherein Mw is determined as described herein.

In another embodiment, the random copolymer of propylene may have a Mnof about 5,000 to about 3,000,000 g/mole, more preferably a Mn of about10,000 to about 1,000,000 g/mol, more preferably a Mn of about 30,000 toabout 500,000 g/mol, more preferably a Mn of about 50,000 to about200,000 g/mol, wherein Mn is determined as described herein.

In a preferred embodiment, the random copolymer of propylene may have aMz of about 10,000 to about 5,000,000 g/mole, more preferably a Mz ofabout 50,000 to about 1,000,000 g/mol, more preferably a Mz of about80,000 to about 500,000 g/mol, more preferably a Mz of about 100,000 toabout 300,000 g/mol, wherein Mz is determined as described herein.

The molecular weight distribution index (MWD=Mw/Mn) of the randomcopolymer of propylene may be about 1.5 to 40.0, more preferably about1.8 to 5 and most preferably about 1.8 to 3. Techniques for determiningthe molecular weight (Mn and Mw) and molecular weight distribution (MWD)may be found in U.S. Pat. No. 4,540,753 (Cozewith, Ju and Verstrate)(which is incorporated by reference herein for purposes of U.S.practices) and references cited therein and in Macromolecules, 1988,volume 21, p 3360 (Verstrate et al.), which is herein incorporated byreference for purposes of U.S. practice, and references cited therein.

In a preferred embodiment, the random copolymer of propylene may have ag′ index value of about 1 to about 1.5, more preferably a g′ of about1.25 to about 1.45, when measured at the Mw of the polymer using theintrinsic viscosity of isotactic polypropylene as the baseline. For useherein, the g′ index is defined as:

$g^{\prime} = \frac{\eta_{b}}{\eta_{1}}$

where η_(b) is the intrinsic viscosity of the random copolymer ofpropylene and η_(l) is the intrinsic viscosity of a linear polymer ofthe same viscosity-averaged molecular weight (M_(v)) of the randomcopolymer of propylene. η_(l)=KM_(v) ^(α), K and α were measured valuesfor linear polymers and should be obtained on the same instrument as theone used for the g′ index measurement.

In some embodiments, the random copolymer of propylene may have acrystallization temperature (Tc) measured with differential scanningcalorimetry (DSC) of about 200° C. or less, more preferably, 150° C. orless.

In other embodiments, the random copolymer of propylene may have adensity of about 0.85 to about 0.95 g/ml, more preferably, about 0.87 to0.92 g/ml, more preferably about 0.88 to about 0.91 g/ml as measured perthe ASTM D-1505 test method at 25° C.

In a preferred embodiment, the random copolymer of propylene may have amelt flow rate (MFR) equal to or greater than 0.2 g/10 min, preferablybetween 2-500 g/10 ml. and more preferably between 20-200 g/10 min, asmeasured according to the ASTM D-1238 test method.

In a preferred embodiment, the random copolymer of propylene may have aheat of fusion (ΔHf) determined according to the procedure described inASTM E 794-85, which is less than 70 J/g, preferably greater than orequal to about 0.5 Joules per gram (J/g), and is less than or equal toabout 25 J/g. Preferably less than or equal to about 20 J/g, preferablyless than or equal to about 15 J/g. Also preferably greater than orequal to about 1 J/g, preferably greater than or equal to about 5 J/gaccording to the procedure described in ASTM E 794-85.

A chiral metallocene catalyst may ensure methyl groups of the propyleneresidues in the random copolymer of propylene have predominantly thesame tacticity. Both syndiotactic and isotactic configuration of thepropylene are possible, though the isotactic polymers may be preferred.The tacticity of the propylene residues leads to an amount ofcrystallinity in the polymers. The relatively low levels ofcrystallinity in the random copolymer of propylene may be derived fromisotactic polypropylene obtained by incorporating alpha-olefincomonomers as described above.

The random copolymer of propylene may be partially crystalline, whichpreferably arises from crystallizable stereoregular propylene sequences.For use herein, the crystallinity of the random copolymer of propylenecan also be expressed in terms of percentage of crystallinity, based onthe heat of fusion of the polymer divided by the thermal energy for thehighest order of polypropylene, which is estimated at 189 J/g (i.e.,100% crystallinity is equal to 189 J/g.) for purposes herein.

The random copolymer of propylene of the present invention preferablyhas a polypropylene crystallinity of about 0.25% to about 15%, morepreferably 0.5 to 25%, more preferably 1 to 20%, more preferably 2 to15%, more preferably from about 0.5% to about 13%, and most preferablyfrom about 0.5% to about 11%.

In addition to this level of crystallinity, the random copolymer ofpropylene preferably has a single broad melting transition. However,suitable random copolymer of propylene polymer may show secondarymelting peaks adjacent to the principal peak, but for purposes herein,such secondary melting peaks are considered together as a single meltingpoint, with the highest of these peaks being considered the meltingpoint of the random copolymer of propylene.

The random copolymer of propylene preferably has a melting point of lessthan 100° C., preferably from about 25° C. to about 75° C., preferablyabout 25° C. to about 65° C., more preferably about 30° C. to about 60°C.

The procedure for Differential Scanning Calorimetry (DSC) is describedas follows: About 6 to 10 mg of a sheet of the polymer pressed atapproximately 200° C. to 230° C. is removed with a punch die. This isannealed at room temperature for 240 hours. At the end of this period,the sample is placed in a Differential Scanning Calorimeter (PerkinElmer 7 Series Thermal Analysis System) and cooled to about −50° C. toabout −70° C. The sample is heated at 20° C./min to attain a finaltemperature of about 200° C. to about 220° C. The thermal output,recorded as the area under the melting peak of the sample which istypically peaked at about 30° C. to about 175° C. and occurs between thetemperatures of about 0° C. and about 200° C. is a measure of the heatof fusion expressed in Joules per gram of polymer. The melting point isrecorded as the temperature of the greatest heat absorption within therange of melting of the sample.

The random copolymer of propylene may have a Mooney viscosity ML(1+4)@125° C., as determined according to ASTM D1646, of less than 100,more preferably less than 75, even more preferably less than 60, mostpreferably less than 30.

The random copolymer of propylene of the present invention preferablycomprises a random crystallizable copolymer having a narrowcompositional distribution. The intermolecular composition distributionof may be determined by thermal fractionation in a solvent such as asaturated hydrocarbon e.g., hexane or heptane. This thermalfractionation procedure is described below. Typically, approximately 75%by weight and more preferably 85% by weight of the polymer is isolatedas one or two adjacent, soluble fraction with the balance of the polymerin immediately preceding or succeeding fractions. Each of thesefractions has a composition (wt % ethylene content) with a difference ofno greater than 20% (relative) and more preferably 10% (relative) of theaverage weight percent (wt %) ethylene content of random copolymer ofpropylene. Thus the random polypropylene copolymer is said to have anarrow compositional distribution if it meets this fractionation testcriteria.

The length and distribution of stereoregular propylene sequences in apreferred random copolymer of propylene is consistent with substantiallyrandom statistical copolymerization. It is well known that sequencelength and distribution are related to the copolymerization reactivityratios. By substantially random, we mean a copolymer for which theproduct of the reactivity ratios is generally 2 or less. In stereoblockstructures, the average length of polypropylene sequences is greaterthan that of substantially random copolymers with a similar composition.Prior art polymers with stereoblock structure have a distribution ofpolypropylene sequences consistent with these blocky structures ratherthan a random substantially statistical distribution. The reactivityratios and sequence distribution of the random copolymer of propylenepolymer may be determined by ¹³C NMR in such as way so as to locate theethylene residues in relation to the neighboring propylene residues.

As outlined herein, to produce random copolymer of propylene with therequired randomness and narrow composition distribution, it is desirableto use (1) a single sited catalyst and (2) a well-mixed, continuous flowstirred tank polymerization reactor which allows only a singlepolymerization environment for substantially all of the polymer chainsof preferred random copolymer of propylene polymers.

A preferred random copolymer of propylene used in the present inventionis described in detail as the “Second Polymer Component (SPC)” inco-pending U.S. applications U.S. Ser. No. 60/133,966, filed May 13,1999, and U.S. Ser. No. 60/342,854, filed Jun. 29, 1999, and describedin further detail as the “Propylene Olefin Copolymer” in U.S. Ser. No.90/346,460, filed Jul. 1, 1999, which are both fully incorporated byreference herein for purposes of U.S. practice.

In addition to one or more comonomers making up the major portion of therandom copolymer of propylene polymer (i.e., alpha-olefins) selectedsuch as, but not limited to, ethylene, alpha-olefins having 4 to 8carbon atoms, and styrenes, random copolymer of propylene polymers, asdescribed above can contain long chain branches, which can optionally begenerated using one or more alpha, omega-dienes. Alternatively, randomcopolymer of propylene may comprise at least one diene, and morepreferably at least one non-conjugated diene, which may aid invulcanization and other chemical modification and/or cross-linkingprocesses. The amount of diene in random copolymer of propylene maypreferably be no greater than about 10 wt %, more preferably no greaterthan about 5 wt %.

In a preferred embodiment, the diene may be selected from the groupconsisting of those that are used for the vulcanization of ethylenepropylene rubbers. Specific examples of preferred dienes includeethylidene norbornene, vinyl norbornene, dicyclopentadiene, and1,4-hexadiene (available from DuPont Chemicals).

In another embodiment, the prSPO of the polymer concentrate may compriserandom copolymer of propylene in the form of a blend of discrete randomcopolymers of propylene. Such blends can include two or morepolyethylene copolymers (as described above), two or more polypropylenecopolymers (as described above), or at least one of each suchpolyethylene copolymer and polypropylene copolymer, so long as each ofthe polymers of the random copolymer of propylene blend wouldindividually qualify as a random copolymer of propylene. Each of therandom copolymers of propylene are described above and the number ofrandom copolymer of propylene in a preferred embodiment may be three orless, more preferably two or less.

In an embodiment of the invention, the random copolymer of propylenepolymer may comprise a blend of two random copolymer of propylenepolymers differing in the olefin content. Preferably, one randomcopolymer of propylene may comprise about 7 to 13 mole % olefin, whilethe other random copolymer of propylene may comprise about 14 to 22 mole% olefin. In an embodiment, the preferred olefin in the random copolymerof propylene is ethylene.

The random copolymer of propylene polymers useful in the instantinvention preferably comprise a particular triad tacticity. The term“tacticity” refers to the stereogenicity in the polymer. For example,the chirality of adjacent monomers can be of either like or oppositeconfiguration. The term “diad” is used herein to designate twocontiguous monomers; thus, three adjacent monomers are referred toherein as a triad. In the instance wherein the chirality of adjacentmonomers is of the same relative configuration, the diad is termedisotactic. In the instance wherein the chirality of adjacent monomers isin an opposite relative configuration, the diad is termed syndiotactic.Another way to describe the configurational relationship is to termcontiguous pairs of monomers having the same chirality as meso (m) andthose of opposite configuration racemic (r).

When three adjacent monomers are of the same configuration, thestereoregularity of the triad is abbreviated as “mm”. If two adjacentmonomers in a three-monomer sequence have the same chirality and that isdifferent from the relative configuration of the third unit, this triadhas ‘mr’ tacticity. An ‘rr’ triad has the middle monomer unit having anopposite configuration from either neighbor. The fraction of each typeof triad in a polymer may be determined, and then multiplied by 100 toindicate the percentage of that type of triad found in the polymer. Thereactivity ratios and sequence distribution of the polymer may bedetermined by ¹³C NMR, which locates the ethylene residues in relationto the neighboring propylene residues.

Random copolymers of propylene have unique propylene tacticity asmeasured by the % meso triad. As shown in detail in U.S. Ser. No.09/108,772, filed Jul. 1, 1998, fully incorporated herein by reference,random copolymer of propylene polymers of this invention have a lower %meso triad for any given ethylene content when compared to U.S. Pat. No.5,504,172. The lower content of % meso triads corresponds to relativelylower crystallinity that translates into better elastomeric propertiessuch as high tensile strength and elongation at break coupled with verygood elastic recovery. Good elastomeric properties are important forsome of the potential applications of the present invention.

Preferred random copolymers of propylene used in embodiments of thepresent invention have a mm tacticity index (m/r), also referred toherein as a propylene tacticity index and/or as mm triad tacticityindex, of at least 75%. The propylene tacticity index, expressed hereinas “m/r”, is determined by ¹³C nuclear magnetic resonance (NMR). Thepropylene tacticity index m/r is calculated as defined in H. N. Cheng,Macromolecules, 17, 1950 (1984). The designation “m” or “r” describesthe stereochemistry of pairs of contiguous propylene groups, “m”referring to meso and “r” to racemic. An m/r ratio of 0 to less than 1.0generally describes a syndiotactic polymer, and an m/r ratio of 1.0 anatactic material, and an m/r ratio of greater than 1.0 an isotacticmaterial. An isotactic material theoretically may have a ratioapproaching infinity, and many by-product atactic polymers havesufficient isotactic content to result in ratios of greater than 50.

In a preferred embodiment, the random copolymers of propylene haveisotactic stereoregular propylene crystallinity. The term“stereoregular” as used herein means that the predominant number, i.e.greater than 80%, of the propylene residues in the polypropyleneexclusive of any other monomer such as ethylene, has the same 1,2insertion and the stereochemical orientation of the pendant methylgroups is the same, either meso or racemic.

Advantaged random copolymers of propylene useful in this invention havean mm triad tacticity index of three propylene units, as measured by ¹³CNMR, of 75% or greater, 80% or greater, 82% or greater, 85% or greater,or 90% or greater. The mm triad tacticity index of a polymer is therelative tacticity of a sequence of three adjacent propylene units, achain consisting of head to tail bonds, expressed as a binarycombination of m and r sequences. For purposes herein, it is expressedfor random copolymers of propylene of the present invention as the ratioof the number of units of the specified tacticity to all of thepropylene triads in the copolymer. The tacticity index (mm fraction) ofa propylene copolymer can be determined from a ¹³C NMR spectrum of thepropylene copolymer and the following formula:

${m\; m\mspace{14mu} {Fraction}} = \frac{{PPP}\left( {m\; m} \right)}{{{PPP}\left( {m\; m} \right)} + {{PPP}({mr})} + {{PPP}({rr})}}$

where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the following three propylene unitchains consisting of head-to-tail bonds:

The ¹³C NMR spectrum of the propylene copolymer is measured as describedin U.S. Pat. No. 5,504,172. The spectrum relating to the methyl carbonregion (19-23 parts per million (ppm)) can be divided into a firstregion (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a thirdregion (19.5-20.3 ppm). Each peak in the spectrum was assigned withreference to an article in the journal Polymer, Volume 30 (1989), page1350. In the first region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (mm) resonates. In thesecond region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (mr) resonates, and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm). In the third region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (rr) resonates, and themethyl group (EPE-methyl group) of a propylene unit whose adjacent unitsare ethylene units resonates (in the vicinity of 19.8 ppm). Thecalculation of the mm triad tacticity is outlined in the techniquesshown in U.S. Pat. No. 5,504,172. Subtraction of the peak areas for theerror in propylene insertions (both 2,1 and 1,3) from peak areas fromthe total peak areas of the second region and the third region, the peakareas based on the 3 propylene units-chains (PPP(mr) and PPP(rr))consisting of head-to-tail bonds can be obtained. Thus, the peak areasof PPP(mm), PPP(mr) and PPP(rr) can be evaluated, and hence the triadtacticity of the propylene unit chain consisting of head-to-tail bondscan be determined. The triad tacticity can be determined from a ¹³C-NMRspectrum of the polymer, as described by J. A. Ewen, “CatalyticPolymerization of Olefins”, (the Ewen method); and Eds. T. Keii, K.Soga; Kodanska Elsevier Pub.; Tokyo, 1986, P 271, and as described indetail in U.S. Patent Application US2004/054086 filed Mar. 18, 2004 onpage 8, in numbered paragraphs [0046] to [0054], all of which areincorporated by is reference herein.

Propylene polymers useful as prSPOs herein are available commerciallyunder the trade name Vistamaxx™ (ExxonMobil, Baytown Tex.). Suitableexamples include: VM 1100, VM1120, VM2100, VM2120, VM2125, VM2210,VM2260, VM2320, VM2330, VM2371, VM3000, VM6100, VM6200.

Preparation of prSPOs:

Random copolymer of propylene useful as soft polyolefins herein can beprepared either in-line or off-line by polymerizing propylene with oneor more of a C₂ or C₅-C₂₀ alpha olefin, most preferably the randomcopolymer of propylene comprises propylene and ethylene. The monomersare advantageously polymerized in the presence of a chiral metallocenecatalyst with an activator and optionally a scavenger. The comonomer orcomonomers used in combination with propylene may be linear and/orbranched. Advantageous linear alpha-olefins include ethylene or C₄ to C₈alpha-olefins, more advantageously ethylene, 1-butene, 1-hexene, and1-octene, ethylene or 1-butene are particularly advantageous.Advantageous branched alpha-olefins include 4-methyl-1-pentene,3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.

In one embodiment, a continuous polymerization process may be used toproduce random copolymer of propylene in-line comprising, for example,propylene and one or more of ethylene, octene, or a diene. Thepolymerization process may use a metallocene catalyst, for example, oneprepared by reacting dimethyl1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9-fluorenyl)hafniumprecursor with dimethylaniliniumtetrakis(pentafluorophenyl)borate as anactivator. An organo-aluminum compound, namely, tri-n-octylaluminum, maybe added as a scavenger to the monomer feed streams prior tointroduction into the polymerization process. For production of morecrystalline polymers, dimethylsilylbis(indenyl)hafnium dimethylprecursor may be used in combination withdimethylaniliniumtetrakis(pentafluorophenyl)borate. Hexane or bulkmonomers may be employed as solvent. In addition, toluene may be addedto increase the solubility of the co-catalyst. The feed is fed to thefirst reactor where the exothermic polymerization reaction is conductedat a reaction temperature between about 50° C. to about 220° C. Hydrogengas may also be added to the reactors as a further molecular weightregulator. If desired, polymer product is transferred to the secondreactor in series, which is also operated at a temperature between about50° C. to 200° C. Note that the one reactor or two reactors in seriesrepresent a single reactor train (in this particular case a plasticizerreactor train) of the disclosed processes. Additional monomers, solvent,metallocene catalyst, and activators can be fed to the second and/oradditional reactors.

In some embodiments, the polymer content leaving the second reactor ispreferably from 8 to 22 weight percent. A heat exchanger then heats thepolymer solution to a temperature of about 220° C. The polymer solutionis then brought to a Lower Critical Solution Temperature (LCST)liquid-liquid phase separator which causes the polymer solution toseparate into two liquid phases—an upper lean phase and a lowerpolymer-rich phase. The upper lean phase contains about 70 wt % of thesolvent and the lower polymer rich phase contains about 30 wt % polymer.The polymer solution then enters a low pressure separator vessel whichoperates at a temperature of about 150° C. and a pressure of 4-10 bar-g(400 to 1000 Pa) and flashes the lower polymer rich phase to removevolatiles and to increase the polymer content to about 76 wt %. A gearpump at the bottom of the flash vessel drives the polymer rich solutionto a List devolatilizer. An extruder is coupled to the end of the Listdevolatilizer whereby the polymer material is transferred to a gear pumpwhich pushes the polymer material through a screen pack. Then thepolymer may be cut into pellets and fed to a water bath. A spin dryermay be used to dry the polymer pellets, which preferably have a finalsolvent content of less than about 0.5 wt %.

As stated above, advantageous random copolymers of propylene of thepresent invention may be prepared by polymerizing propylene and at leastone C₂ or C₄-C₂₀ alpha olefin in the presence of a chiral metallocenecatalyst with an activator and optional scavenger, most preferablyethylene and propylene. The terms “metallocene” and “metallocenecatalyst precursor” are terms known in the art to mean compoundspossessing a Group IV, V, or VI transition metal M, with acyclopentadienyl (Cp) ligand or ligands which may be may be substituted,at least one non-cyclopentadienyl-derived ligand X, and zero or oneheteroatom-containing ligand Y, the ligands being coordinated to M andcorresponding in number to the valence thereof. The metallocene catalystprecursors generally require activation with a suitable activator (alsoreferred to as an co-catalyst) in order to yield an active metallocenecatalyst or catalyst system. An active metallocene catalyst refersgenerally to an organometallic complex with a vacant coordination sitethat can coordinate, insert, and polymerize olefins.

Metallocenes for making soft random copolymers of propylene hereininclude bridged and unbridged biscyclopentadienyl complexes where thecyclopentadienyl group are, independently, a substituted orunsubstituted cyclopentadienyl group, a substituted or unsubstitutedindenyl group, or a substituted or unsubstituted fluorenyl group.Metallocenes include those represented by the formula: TCpCpMX₂, where Tis a bridging group such as a dialkyl silicon group (such asdimethylsilyl) or a hydrocarbyl group (such as methyl, ethyl, orpropyl), each Cp is, independently a substituted or unsubstitutedcyclopentadienyl group, a substituted or unsubstituted indenyl group(preferably a 2, 4 or 2, 4, 7 substituted indenyl group), or asubstituted or unsubstituted fluorenyl group, M is a group 4 metal(preferably Hf, Zr or Ti) and each X is independently a halogen orhydrocarbyl group (such as chlorine, bromine, methyl, ethyl, propyl,butyl, or phenyl).

Metallocenes for making soft random copolymers of propylene hereininclude cyclopentadienyl (Cp) complexes which have two Cp ring systemsfor ligands. The Cp ligands preferably form a “bent sandwich complex”with the metal and are preferably locked into a rigid configurationthrough a bridging group. Such preferred cyclopentadienyl complexes mayhave the general formula:

(Cp¹R¹m)R³n(Cp²R²p)MXq

wherein Cp¹ of ligand (Cp¹R¹m) and Cp² of ligand (Cp²R²p) are preferablythe same, R¹ and R² each are, independently, a halogen or a hydrocarbyl,halocarbyl, hydrocarbyl-substituted organometalloid orhalocarbyl-substituted organometalloid group containing up to 20 carbonatoms;

m is preferably 1 to 5;

p is preferably 1 to 5;

preferably two R¹ and/or R² substituents on adjacent carbon atoms of thecyclopentadienyl ring associated there can be joined together to form aring containing from 4 to 20 carbon atoms;

R³ is a bridging group;

n is the number of atoms in the direct chain between the two ligands andis preferably 1 to 8, most preferably 1 to 3;

M is a transition metal having a valence of from 3 to 6, preferably fromgroup 4, 5, or 6 of the periodic table of the elements and is preferablyin its highest oxidation state,

each X is a non-cyclopentadienyl ligand and is, independently, ahydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substitutedorganometalloid, oxyhydrocarbyl-substituted organometalloid orhalocarbyl-substituted organometalloid group containing up to 20 carbonatoms; and

q is equal to the valence of M minus 2.

Numerous examples of the biscyclopentadienyl metallocenes describedabove for the invention are disclosed in U.S. Pat. Nos. 5,324,800;5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714; 4,871,705;4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243, 5,278,264; 5,296,434;and 5,304,614, all of which are incorporated by reference for purposesof U.S. patent practice. Illustrative, but not limiting examples ofpreferred biscyclopentadienyl metallocenes of the type described abovefor the invention include the racemic isomers of:

μ-(CH₃)₂Si(indenyl)₂M(Cl)₂

μ-(CH₃)₂Si(indenyl)₂M(CH₃)₂

μ-(CH₃)₂Si(tetrahydroindenyl)₂M(Cl)₂

μ-(CH₃)₂Si(tetrahydroindenyl)₂M(CH₃)₂

μ-(CH₃)₂Si(indenyl)₂M(CH₂CH₃)₂

μ-(C₆H₅)₂C(indenyl)₂M(CH₃)₂;

wherein M may include Zr, H_(f), and/or Ti.

These metallocenes may advantageously be used in combination with one ormore aluminoxanes (preferably methyl aluminoxane, or modified methylaluminoxane) and or one or more ionic activators such asN,N-dimethylanilinium tetraphenylborate, N,N-dimethylaniliniumtetrakis(penta-fluorophenyl)borate, diphenylcarbeniumtetra(perfluorophenyl)borate, or N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate.

IV.B. Ethylene-Rich Soft Polyolefins

An ethylene-rich soft polyolefin (erSPO) is an ethylene copolymercomprising at least 50 wt % ethylene and having the properties of a softpolyolefin. In some embodiments, the erSPO comprises at least 60 wt %ethylene, or at least 70 wt % ethylene, or at least 80 wt % ethylene, orat least 90 wt % ethylene.

In one embodiment, the erSPO may comprise 10 to 50 wt %, or 10 to 40 wt%, or 10 to 30 wt %, or 10 to 20 wt % of a C₃-C₂₀ comonomer. In anotherembodiment, erSPOs advantageously have a composition distributionbreadth index (CDBI) above 90%, even more preferably above 95%. Inanother embodiment, erSPOs has a density of 0.86 to 0.925 g/mL and aCDBI of over 90%, preferably between 95% and 99%. In another embodiment,erSPOs has a MI of 0.1 to 100 g/10 min, preferably 0.5 to 50 g/10 min,more preferably 0.8 to 30 g/10 min.

In one embodiment, the erSPOs are metallocene polyethylenes (mPE's). ThemPE homopolymers or copolymers may be produced using mono- orbis-cyclopentadienyl transition metal catalysts in combination with anactivator of aluminoxane and/or a non-coordinating anion in homogeneoussupercritical, solution, or slurry process. Advantageously, thepolymerization is performed in a homogeneous supercritical or solutionprocess. The catalyst and activator may be supported or unsupported andthe cyclopentadienyl rings by may substituted or unsubstituted. Severalcommercial products produced with such catalyst/activator combinationsare commercially available from ExxonMobil Chemical Company in Baytown,Tex. under the tradename EXACT™. For more information on the methods andcatalysts/activators to produce such mPE homopolymers and copolymers seeWO 94/26816; WO 94/03506; EPA 277 003; EPA 277 004; U.S. Pat. No.5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat.No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129 368; U.S.Pat. No. 5,264,405; EPA 520 732; WO 92 00333; U.S. Pat. No. 5,096,867;U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495375; EPA 500 944; EPA 570 982; WO 91/09882; WO 94/03506 and U.S. Pat.No. 5,055,438.

Examples of Exact Plastomers suitable for use herein as soft polyolefinsinclude:

EXACT-Plastomers EXACT- Melt- DSC-Melting Plastomers Density Index PeakGrade Composition (g/mL) (g/10 min) (° C.), 10° C./min 3024Ethylene/butene 0.905 4.5 98 3035 Ethylene/butene 0.900 3.5 88 3128Ethylene/butene 0.900 1.2 92 4006 Ethylene/butene 0.880 10 60 4011Ethylene/butene 0.888 2.2 70 4033 Ethylene/butene 0.880 0.8 60 4049Ethylene/butene 0.873 4.5 55 3040 Ethylene/hexene 0.900 16.5 96 3131Ethylene/hexene 0.900 3.5 95 3132 Ethylene/hexene 0.900 1.2 96 3139Ethylene/hexene 0.900 7.5 95 4056 Ethylene/hexene 0.883 2.2 72 4151Ethylene/hexene 0.895 2.2 89 0201 Ethylene/octene 0.902 1.1 95 0203Ethylene/octene 0.902 3.0 95 0210 Ethylene/octene 0.902 10 96 0230Ethylene/octene 0.902 30 95 5061 Ethylene/octene 0.868 0.5 53 5062Ethylene/octene 0.860 0.5 43 5101 Ethylene/octene 0.902 1.1 98 5171Ethylene/octene 0.870 1.0 55 5181 Ethylene/octene 0.882 1.1 73 5361Ethylene/octene 0.860 3.0 36 5371 Ethylene/octene 0.870 5.0 64 8201Ethylene/octene 0.882 1.1 67 8203 Ethylene/octene 0.882 3.0 73 8210Ethylene/octene 0.882 10 67 8230 Ethylene/octene 0.882 30 77

Other suitable erSPOs include low-density polyethylene (LDPE),linear-low density polyethylene (LLDPE), and very-low densitypolyethylene (vLDPE) type polyethylene polymers and copolymers whichhave the properties of a soft polyolefin.

III.C. Elastomeric Soft Polyolefins

The SPO may be a cross-linkable polyolefin elastomer containingethylene, propylene, and optionally one or more diene. Illustrativeexamples include ethylene-propylene (EP) elastomers andethylene-propylene-diene (EPDM) elastomers.

A suitable EP elastomer can have an ethylene content of 40 to 80 wt %(preferably 45 to 75 wt %, preferably 50 to 70 wt %). A suitable EPelastomer can also have an ethylene content of 5 to 25 wt % (preferably10 to 20 wt %). A suitable EPDM elastomer can have an ethylene contentof 40 to 80 wt % (preferably 45 to 75 wt %, preferably 50 to 70 wt %)and a diene content of less than 15 wt % (preferably 0.5 to 15 wt %,preferably 1 to 12 wt %, preferably 2 to 10 wt %, preferably 3 to 9 wt%). In one or more embodiments, a suitable EPDM elastomer can have anethylene content of 5 to 25 wt % (preferably 10 to 20 wt %). In otherembodiments, a suitable EPDM elastomer can have a diene content of 0.1to 3 wt % (preferably 0.3 to 2 wt %), or 0.3 to 10 wt % (preferably 1 to5 wt %). Suitable dienes can have at least two unsaturated bonds, atleast one of which can be incorporated into a polymer, and can bestraight chained, branched, cyclic, bridged ring, bicyclic, etc.;preferably the unsaturated bonds are nonconjugated. Preferred dienesinclude 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB),divinyl benzene (DVB), dicyclopentadiene (DCPD), and 1,4-hexadiene.

Preferred EP and EPDM elastomers can have one or more of the followingproperties: a density of 0.885 g/cm³ or less (preferably 0.88 g/cm³,preferably 0.87 g/cm³ or less, preferably 0.865 g/cm³ or less,preferably 0.86 g/cm³ or less, preferably 0.855 g/cm³ or less); and/or aheat of fusion (H_(f)) of less than 70 J/g (preferably less than 60 J/g,preferably less than 50 J/g, preferably less than 40 J/g, preferablyless than 30 J/g, preferably less than 20 J/g, preferably less than 10J/g, preferably less than 5 J/g, preferably indiscernible); and/or anethylene or propylene crystallinity of less than 15 wt % (preferablyless than 10 wt %, preferably less than 5 wt %, preferably less than 2wt %, preferably undetectable); and/or a melting point (T_(m)) of 120°C. or less (preferably 100° C. or less, preferably 80° C. or less,preferably 70° C. or less, preferably 60° C. or less, preferably 50° C.or less, preferably 40° C. or less, preferably 35° C. or less,preferably undetectable); and/or a glass transition temperature (T_(g))of −20° C. or less (preferably −30° C. or less, preferably −40° C. orless, preferably −50° C. or less, preferably −60° C. or less); and/or aM_(w) of 50 to 5,000 kg/mol (preferably 100 to 3,000 kg/mol, preferably150 to 2,000 kg/mol, preferably 200 to 1,000 kg/mol); and/or aM_(w)/M_(n) of 1.5 to 40 (preferably 1.6 to 30, preferably 1.7 to 20,preferably 1.8 to 10); and/or a Mooney viscosity, ML(1+4) at 125° C. of1 to 100 (preferably 5 to 95, preferably 10 to 90, preferably 15 to 85,preferably 20 to 80).

In one or more embodiments, the EP or EPDM elastomer can befunctionalized. For example, the ethylene-propylene elastomers can befunctionalized by reacting with organic compounds with polar moieties,such as amine-, carboxy-, and/or epoxy-moieties. Examples includemaleated EP and EPDM elastomers.

Suitable ethylene-propylene elastomers include those available fromExxonMobil Chemical under the Vistalon®, and Exxelor™ tradenames.

III.D. Other Soft Polyolefins

Other suitable soft polyolefins include propylene homopolymer and/orpropylene copolymers that have been contacted with less than about 10 wt% of a highly crystalline branched or coupled polymeric nucleating agentunder nucleation conditions. Such polymers may be produced with anactivated non metallocene, metal-centered, heteroaryl ligand catalyst,as described in WO 03/040095 on pages 21-52. Examples include apropylene-ethylene copolymer comprising at least about 60 weight percentof units derived from propylene and at least about 0.1 weight percent ofunits derived from ethylene.

Particular embodiments of such polymers include a propylene-ethylenecopolymer comprising at least about 60 weight percent of units derivedfrom propylene and at least about 0.1 weight percent of units derivedfrom ethylene, as disclosed in WO 03/040095 A2 at page 9.

Other polymers useful as the soft polyolefin include one or morepolypropylene copolymers having elastic properties. Such preferredpropylene copolymers having elastic properties may be prepared accordingthe procedures in WO 02/36651 which is incorporated by reference here.Likewise, the SPO may comprise polymers consistent with those describedin WO 03/040202, WO 03/040095, WO 03/040201, WO 03/040233, and/or WO03/040442. Additionally, the SPO may comprise polymers consistent withthose described in EP 1 233 191, and U.S. Pat. No. 6,525,157.

Other polymers useful as the soft polyolefin include homopolymer andcopolymers of butene-1; isobutylene-based elastomers such as butyl,halobutyl, and functionalized (e.g., by halogenation) orunfunctionalized copolymers of isobutylene and one or more styreniccomonomer such as p-methylstyrene; styrenic block copolymers such asSBS, SIS, SEBS, and SEPS; and thermoplastic vulcanizates. The SPO mayalso be a blend of one or more individual SPO components as describedabove.

The above identified composition and properties described for thevarious in-line produced and off-line produced plasticizers of theinstant invention may also be combined to form numerous combinations ofplasticizer types and properties that have not be specifically set forthabove, but still fall within the scope of the present disclosure.

Plasticized Polymer Blends and Polymer Additives:

In one embodiment, the plasticized polymer blends produced by the fluidphase in-line polymer blending process disclosed herein include a singlehigh molecular base polymer blend component made in one of the parallelreactor trains and a single plasticizer blend component produced in asecond parallel reactor train.

In one form, the plasticizer is an alpha-olefin oligomer fluid with amolecular weight of 20,000 g/mol or less, 15,000 g/mol or less, 10,000g/mol or less, or 5,000 g/mol or less. In another embodiment, thealpha-olefin oligomer has a molecular weight of 500 to 5,000 g/mol. Atthese low molecular weights, the alpha olefin oligomer fluids aremiscible to a degree with the polymer blend components disclosed hereinto provide a plasticizing effect. In another embodiment, the plasticizeris a low glass transition temperature polymeric material with a glasstransition temperature of less than 0° C., or less than −5° C., or lessthan −25° C. Partial miscibility of the low glass transition temperaturepolymeric material with the high molecular polymer blend component isadvantageous.

In another embodiment, the plasticized polymer blends produced producedby the fluid phase in-line polymer blending process disclosed hereininclude a single high molecular weight base polymer blend component madein one of the parallel reactor trains and two or more In-Line-ProducedPlasticizer blend components.

In another embodiment, the plasticized polymer blends produced by thefluid phase in-line polymer blending process disclosed herein includetwo or more high molecular weight base polymer components, including butnot limited to, thermoplastic polymer(s) and/or elastomer(s) blendedwith one or more In-Line-Produced Plasticizer blend components.

In yet another embodiment, any of the preceding embodiments includingone or more high molecular weight base polymers and one or moreplasticizer components produced and blended in-line may further includeone or more other plasticizer components that are not produced in-line(off-line-produced plasticizer component), but blended in-line. Theseplasticizers which are not produced in-line because they are notconducive to such may still be in-line blended with the plasticizedpolymer components from the previous three embodiments from one or morepolymer/additive storage tanks. Plasticizers that may not be reactedin-line, but may be in-line blended, include, but are not limited to thefollowing: paraffin oils and waxes (n-paraffins, isoparaffins, paraffinblends), dearomatized aliphatic hydrocarbons, process oils, high purityhydrocarbon fluids, lubricant basestocks, other oils, phthalates,mellitates and adipates, etc.

A “thermoplastic polymer(s)” is a polymer that can be melted by heat andthen cooled with out appreciable change in properties. Thermoplasticpolymers typically include, but are not limited to, polyolefins,polyamides, polyesters, polycarbonates, polysulfones, polyacetals,polylactones, acrylonitrile-butadiene-styrene resins, polyphenyleneoxide, polyphenylene sulfide, styrene-acrylonitrile resins, styrenemaleic anhydride, polyimides, aromatic polyketones, or mixtures of twoor more of the above. The disclosed processes make and blend polyolefinbase polymer components in-line. Polyolefins include, but are notlimited to, polymers comprising one or more linear, branched or cyclicC₂ to C₄₀ olefins, polymers comprising propylene copolymerized with oneor more C₂ or C₄ to C₄₀ olefins, C₃ to C₂₀ alpha olefins, or C₃ to C₁₀α-olefins. Also, polyolefins include, but are not limited to, polymerscomprising ethylene including but not limited to ethylene copolymerizedwith a C₃ to C₄₀ olefin, a C₃ to C₂₀ alpha olefin, propylene and/orbutene.

“Elastomers” encompass all natural and synthetic rubbers, includingthose defined in ASTM D1566). Examples of useful elastomers include, butare not limited to, ethylene propylene rubber, ethylene propylene dienemonomer rubber, styrenic block copolymer rubbers (including SI, SIS, SB,SBS, SEBS and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).

In another form, the plasticized polymer blends produced herein mayinclude one or more of isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene and/or butene and/or hexene, polybutene, ethylene vinylacetate, low density polyethylene (density 0.915 to less than 0.935g/mL), linear low density polyethylene, ultra low density polyethylene(density 0.86 to less than 0.90 g/mL), very low density polyethylene(density 0.90 to less than 0.915 g/mL), medium density polyethylene(density 0.935 to less than 0.945 g/mL), high density polyethylene(density 0.945 to 0.98 g/mL), ethylene vinyl acetate, ethylene methylacrylate, copolymers of acrylic acid, polymethylmethacrylate or anyother polymers polymerizable by a high-pressure free radical process,polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer,styrenic block copolymers, polyamides, polycarbonates, PET resins,crosslinked polyethylene, polymers that are a hydrolysis product of EVAthat equate to an ethylene vinyl alcohol copolymer, polymers of aromaticmonomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidinefluoride, polyethylene glycols and/or polyisobutylene.

In another form, elastomers are blended using the processes disclosedherein to form rubber-toughened compositions. In some forms, the rubbertoughened composition is a two (or more) phase system where theelastomer is a discontinuous phase and the polymer produced herein is acontinuous phase. This blend may be combined with tackifiers and/orother additives as described herein.

In another form, the plasticized polymer blends produced by theprocesses disclosed herein may include elastomers or other soft polymersto form impact copolymers. In some forms, the blend is a two (or more)phase system where the elastomer or soft polymer is a discontinuousphase and other polymer(s) is a continuous phase. The blends producedherein may be combined with tackifiers and/or other additives asdescribed herein.

In some forms, the plasticized polymers blends disclosed herein includemetallocene polyethylenes (mPEs) or metallocene polypropylenes (mPPs).The mPE and mPP homopolymers or copolymers are typically produced usingmono- or bis-cyclopentadienyl transition metal catalysts in combinationwith an activator of aluminoxane and/or a non-coordinating anion insolution, slurry, high pressure or gas phase. The catalyst and activatormay be supported or unsupported and the cyclopentadienyl rings may besubstituted or unsubstituted. Several commercial products produced withsuch catalyst/-activator combinations are commercially available fromExxonMobil Chemical Company in Baytown, Tex. under the tradenamesEXCEED™, ACHIEVE™ and EXACT™. For more information on the methods andcatalysts/activators to produce such homopolymers and copolymers see WO94/26816; WO 94/03506; EPA 277 003; EPA 277 004; U.S. Pat. No.5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat.No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129 368; U.S.Pat. No. 5,264,405; EPA 520 732; WO 92 00333; U.S. Pat. No. 5,096,867;U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495375; EPA 500 944; EPA 570 982; WO 91/09882; WO 94/03506 and U.S. Pat.No. 5,055,438.

In some forms the plasticized polymer blends produced by the processesdisclosed herein include one or more high molecular weight base polymersat from 10 to 99.9 wt %, based upon the weight of the plasticizer andpolymers in the blend, or 20 to 99.9 wt %, or at least 30 to 99.9 wt %,or at least 40 to 99.9 wt %, or at least 50 to 99.9 wt %, or at least 60to 99.9 wt %, or at least 70 to 99.9 wt % with plasticizers and otherpolymer additives constituting the remainder of the blend. In one form,the one or more plasticizer blend components are present in theplasticized polymer blend at lower limits of 0.1 wt %, or 0.25 wt %, or0.5 wt %, or 0.75 wt %, or 1 wt %, or 2 wt %, or 5 wt %, or 10 wt %, 15wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt % based on theoverall weight of the plasticized polymer blend. In another form, theone or more plasticizer blend components are present in the plasticizedpolymer blend at upper limits of 20 wt %, or 25 wt %, or 30 wt %, or 35wt %, or 40 wt %, or 45 wt %, or 50 wt %, or 60 wt %, 70 wt %, or 80 wt%, or 90 wt % based on the overall weight of the plasticized polymerblend.

In another form, in-line plasticized polymer blends are produced frompropylene-based base polymers and plasticizers made at homogeneouspolymerization conditions, particularly at bulk homogeneouspolymerization conditions, such as bulk homogeneous supercritical orbulk solution polymerization, and comprise the following:

-   (a) 10-20 wt % of isotactic polypropylene with 0.8-10,000 g/10 min    MFR and melting peak temperatures of 80-165° C. plus 80-90 wt %    crystallizable ethylene-propylene copolymer comprising 10-16 wt %    ethylene content and 0.8-100 g/10 min MFR or-   (b) 15-90 wt % of isotactic polypropylene with 0.8-10,000 dg/min MFR    and melting peak temperatures of 80-165° C. plus 10-85 wt %    propylene copolymer of isotactic polypropylene crystallinity    comprising 1-20 wt % ethylene or 1-40 wt % hexene-1 or 1-30 wt    butene-1 content and 0.8-100 g/10 min MFR or-   (c) 10-30 wt % of isotactic polypropylene with 0.8-10,000 dg/min MFR    and melting peak temperatures of 80-165° C. plus 90-70 wt %    low-crystallinity (0-30 J/g) homo- or copolymer with MFR of 0.8-500    g/10 min or

The in-line-plasticized polymer blends produced by the process disclosedherein may be also blended with other polymers and additives using thein-line blending process for other polymers and additives depicted inFIG. 11, in an extrusion process downstream of in-linepolymerization/separation/blending processes disclosed herein, orblended in an off-line compounding process.

Any of the above polymers included in the in-line polymer blendsproduced by the processes disclosed herein may be functionalized.Functionalized means that the polymer has been contacted with anunsaturated acid or anhydride. Forms of unsaturated acids or anhydridesinclude any unsaturated organic compound containing at least one doublebond and at least one carbonyl group. Representative acids includecarboxylic acids, anhydrides, esters and their salts, both metallic andnon-metallic. The organic compound contains an ethylenic unsaturationconjugated with a carbonyl group (—C═O). Non-limiting examples includemaleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methylcrotonic, and cinnamic acids as well as their anhydrides, esters andsalt derivatives. Maleic anhydride is one particular form. Theunsaturated acid or anhydride is present at about 0.1 wt % to about 5 wt%, or at about 0.5 wt % to about 4 wt %, or at about 1 to about 3 wt %,based upon the weight of the hydrocarbon resin and the unsaturated acidor anhydride.

Tackifiers may also be blended either in-line by the processes disclosedherein (see FIG. 11), in-line via an extrusion process downstream ofin-line polymerization/separation/blending processes disclosed herein,or in an off-line compounding process. Examples of useful tackifiersinclude, but are not limited to, aliphatic hydrocarbon resins, aromaticmodified aliphatic hydrocarbon resins, hydrogenated polycyclopentadieneresins, polycyclopentadiene resins, gum rosins, gum rosin esters, woodrosins, wood rosin esters, tall oil rosins, tall oil rosin esters,polyterpenes, aromatic modified polyterpenes, terpene phenolics,aromatic modified hydrogenated polycyclopentadiene resins, hydrogenatedaliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenatedterpenes and modified terpenes, and hydrogenated rosin esters. In someembodiments the tackifier is hydrogenated. In other embodiments thetackifier is non-polar. Non-polar tackifiers are substantially free ofmonomers having polar groups. The polar groups are generally notpresent; however, if present, they are not present at more that 5 wt %,or not more that 2 wt %, or no more than 0.5 wt %. In some embodiments,the tackifier has a softening point (Ring and Ball, as measured by ASTME-28) of 80° C. to 140° C., or 100° C. to 130° C. In some embodimentsthe tackifier is functionalized. By functionalized is meant that thehydrocarbon resin has been contacted with an unsaturated acid oranhydride. Useful unsaturated acids or anhydrides include anyunsaturated organic compound containing at least one double bond and atleast one carbonyl group. Representative acids include carboxylic acids,anhydrides, esters and their salts, both metallic and non-metallic. Theorganic compound may contain an ethylenic unsaturation conjugated with acarbonyl group (—C═O). Non-limiting examples include maleic, fumaric,acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, andcinnamic acids as well as their anhydrides, esters and salt derivatives.Maleic anhydride is particularly useful. The unsaturated acid oranhydride may be present in the tackifier at about 0.1 wt % to 10 wt %,or at 0.5 wt % to 7 wt %, or at 1 to 4 wt %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.

The tackifier, if present, is typically present at 1 wt % to 50 wt %,based upon the weight of the blend, or 10 wt % to 40 wt %, or 20 wt % to40 wt %. Generally however, tackifier is not present, or if present, ispresent at less than 10 wt %, or less than 5 wt %, or at less than 1 wt%.

In another form, the plasticized polymer blends produced by theprocesses disclosed herein further comprise a crosslinking agent. Thecrosslinking agent may be blended either in-line by the processesdisclosed herein (see FIG. 11), in-line via an extrusion processdownstream of in-line polymerization/separation/blending processesdisclosed herein, or in an off-line compounding process. Usefulcrosslinking agents include those having functional groups that canreact with the acid or anhydride group and include alcohols, multiols,amines, diamines and/or triamines. Non-limiting examples of crosslinkingagents useful include polyamines such as ethylenediamine,diethylenetriamine, hexamethylenediamine, diethylaminopropylamine,and/or menthanediamine.

In another form, the plasticized polymer blends produced by theprocesses disclosed herein, and/or blends thereof, further comprisetypical additives known in the art such as fillers, cavitating agents,antioxidants, surfactants, adjuvants, other plasticizers, block,antiblock, color masterbatches, pigments, dyes, processing aids, UVstabilizers, neutralizers, lubricants, waxes, nucleating agents and/orclarifying agents. These additives may be present in the typicallyeffective amounts well known in the art, such as 0.001 wt % to 10 wt %.These additive may be blended either in-line by the processes disclosedherein (see FIG. 11), in-line via an extrusion process downstream ofin-line polymerization/separation/blending processes disclosed herein,or in an off-line compounding process.

Useful fillers, cavitating agents and/or nucleating agents includetitanium dioxide, calcium carbonate, barium sulfate, silica, silicondioxide, carbon black, sand, glass beads, mineral aggregates, talc, clayand the like. Nucleating agents of the non-clarifying type include, butare not limited to, sodium benzoate, Amfine NA 11, Amfine NA 21, andMilliken HPN 68.

Useful antioxidants and UV stablilizers include phenolic antioxidants,such as Irganox 1010, Irganox 1076 both available from Ciba-Geigy. Oilsmay include paraffinic or naphthenic oils such as Primol 352, or Primol876 available from ExxonMobil Chemical France, S. A. in Paris, France.The oils may include aliphatic naphthenic oils, white oils or the like.

Useful processing aids, lubricants, waxes, and/or oils include lowmolecular weight products such as wax, oil or low M_(n) polymer, (lowmeaning below M_(n) of 5000, or below 4000, or below 3000, or below2500). Useful waxes include polar or non-polar waxes, functionalizedwaxes, polypropylene waxes, polyethylene waxes, and wax modifiers.

Useful functionalized waxes include those modified with an alcohol, anacid, or a ketone. Functionalized means that the polymer has beencontacted with an unsaturated acid or anhydride. Useful unsaturatedacids or anhydrides include any unsaturated organic compound containingat least one double bond and at least one carbonyl group. Representativeacids include carboxylic acids, anhydrides, esters and their salts, bothmetallic and non-metallic. The organic compound may contain an ethylenicunsaturation conjugated with a carbonyl group (—C═O). Non-limitingexamples include maleic, fumaric, acrylic, methacrylic, itaconic,crotonic, alpha-methyl crotonic, and cinnamic acids as well as theiranhydrides, esters and salt derivatives. Maleic anhydride isparticularly useful. The unsaturated acid or anhydride may be present at0.1 wt % to 10 wt %, or at 0.5 wt % to 7 wt %, or at 1 to 4 wt %, basedupon the weight of the hydrocarbon resin and the unsaturated acid oranhydride. Examples include waxes modified by methyl ketone, maleicanhydride or maleic acid. Low Mn polymers include polymers of loweralpha olefins such as propylene, butene, pentene, hexene and the like. Auseful polymer includes polybutene having an Mn of less than 1000 g/mol.An example of such a polymer is available under the trade name PARAPOL™950 from ExxonMobil Chemical Company. PARAPOL™ 950 is a liquidpolybutene polymer having an Mn of 950 g/mol and a kinematic viscosityof 220 cSt at 100° C., as measured by ASTM D 445.

Useful clarifying agents include, but are not limited to, thebenzalsorbitol family of clarifiers, and more particularlydibenzalsorbitol (Millad 3905), di-p-methylbenzalsorbitol (Milliad3940), and bis-3,4-dimethylbenzalsorbitol (Milliad 3988).

Applications:

The plasticized polymer blends produced by the processes disclosedherein are typically used in any known thermoplastic or elastomerapplication. Non-limiting examples include uses in molded parts, films,tapes, sheets, tubing, hose, sheeting, wire and cable coating,adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elasticfibers, nonwovens, spunbonds, sealants, surgical gowns and medicaldevices. The plasticized polymer blends produced by the processesdisclosed herein are particularly advantageous in applications requiringtoughness, flexibility, and impact resistance at low temperatures.Non-limiting exemplary applications include polyolefin based parts usedin appliances (i.e. refrigerators, and freezers) as wells as parts usedin cold temperature environments.

Applicants have attempted to disclose all embodiments and applicationsof the disclosed subject matter that could be reasonably foreseen.However, there may be unforeseeable, insubstantial modifications thatremain as equivalents. While the present invention has been described inconjunction with specific, exemplary embodiments thereof, it is evidentthat many alterations, modifications, and variations will be apparent tothose skilled in the art in light of the foregoing description withoutdeparting from the spirit or scope of the present disclosure.Accordingly, the present disclosure is intended to embrace all suchalterations, modifications, and variations of the above detaileddescription.

All patents, test procedures, and other documents cited herein,including priority documents, are fully incorporated by reference to theextent such disclosure is not inconsistent with this invention and forall jurisdictions in which such incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.All numerical values within the detailed description and the claimsherein are also understood as modified by “about.”

1. An in-line blending process for plasticized polymers comprising: (a)providing two or more reactor trains configured in parallel and ahigh-pressure separator downstream fluidly connected to the two or morereactor trains configured in parallel, wherein one or more of thereactor trains produces one or more base polymers and one or more of thereactor trains produces one or more plasticizers; (b) contacting in thetwo or more reactor trains configured in parallel 1) olefin monomershaving two or more carbon atoms 2) one or more catalyst systems, 3)optional one or more comonomers, 4) optional one or more scavengers, and5) optional one or more diluents or solvents, wherein at least one ofthe reactor trains configured in parallel is at a temperature above thesolid-fluid phase transition temperature of the polymerization systemand a pressure no lower than 10 MPa below the cloud point pressure ofthe polymerization system and less than 1500 MPa, wherein thepolymerization system for each reactor train is in its dense fluid stateand comprises the olefin monomers, any comonomer present, any diluent orsolvent present, any scavenger present, and the polymer product, whereinthe catalyst system for each reactor train comprises one or morecatalyst precursors, one or more activators, and optionally, one or morecatalyst supports, wherein the one or more catalyst systems are chosenfrom Ziegler-Natta catalysts, metallocene catalysts, nonmetallocenemetal-centered, heteroaryl ligand catalysts, late transition metalcatalysts, and combinations thereof, (c) forming an unreduced polymer orunreduced plasticizer reactor effluent including a homogeneous fluidphase polymer-monomer mixture in one or more parallel reactor trains anda homogeneous fluid phase plasticizer-monomer mixture in one or moreparallel reactor trains; (d) passing the reactor effluents comprisingthe homogeneous fluid phase polymer-monomer mixture andplasticizer-monomer mixture from each parallel reactor train through thehigh-pressure separator for product blending and product-feedseparation; (e) maintaining the temperature and pressure within thehigh-pressure separator above the solid-fluid phase transition point butbelow the cloud point pressure and temperature to form a fluid-fluidtwo-phase system comprising a plasticized polymer-rich blend phase and amonomer-rich phase; and (f) separating the monomer-rich phase from theplasticized polymer-rich blend phase in the high pressure separator toform a plasticized polymer blend and a separated monomer-rich phase. 2.The process of claim 1 wherein in (b) the polymerization systems for thetwo or more reactor trains configured in parallel are at temperaturesabove the solid-fluid phase transition temperatures and pressures nolower than 10 MPa below the cloud point pressures and less than 1500MPa.
 3. The process of claim 1 wherein in (b) the polymerization systemsfor the two or more reactor trains configured in parallel are attemperatures above the solid-fluid phase transition temperatures andpressures no lower than 10 MPa below the cloud point pressures and lessthan 1500 MPa, and comprise less than 40 wt % of optional one or morediluents or solvents.
 4. The process of claim 1 wherein in (b) thepolymerization systems for the two or more reactor trains configured inparallel are at temperatures above the solid-fluid phase transitiontemperatures and pressures no lower than 10 MPa below the cloud pointpressures and less than 1500 MPa, and are above their criticaltemperatures and critical pressures.
 5. The process of claim 1 whereinin (b) the polymerization systems for the two or more reactor trainsconfigured in parallel are at temperatures above the solid-fluid phasetransition temperatures and pressures no lower than 10 MPa below thecloud point pressures and less than 1500 MPa, comprise less than 40 wt %of optional one or more diluents or solvents, and are above theircritical temperatures and critical pressures.
 6. The process of claim 1wherein the two or more reactor trains configured in parallel of (b)includes one or more reactor trains operating at a temperature below thesolid-fluid phase transition temperature of the polymerization systemforming solid polymer particles and the polymerization system comprisesless than 40 wt % of optional one or more diluents or solvents.
 7. Theprocess of claim 1 wherein the olefin monomers having two or more carbonatoms of (b) comprise propylene.
 8. The process of claim 1 wherein thecombined olefin monomers and optional one or more comonomers of (b) arepresent in a combined feed to the one or more polymerization reactors ofone or more reactor trains at 40 wt % or more.
 9. The process of claim 1wherein the olefin monomers and optional one or more comonomers of (b)comprise one or more of ethylene, propylene, butenes, hexenes, octenes,decenes, or dodecenes.
 10. The process of claim 1 further comprisingremoving low molecular weight oligomers, low molecular weight polymers,solvent/diluent or combinations thereof from the separated monomer-richphase of (f) through the use of at least one knock-out pot, at least oneseparation tower, or a combination thereof.
 11. The process of claim 1further comprising providing one or more storage tanks, and feeding fromthe one or more storage tanks one or more polymers, one or more off-lineproduced plasticizers and/or one or more polymer additives to theprocess after (c).
 12. The process of claim 11 further comprisingfeeding the polymer-rich phase of the high-pressure separator of (a)containing the plasticized polymer blend to one or more low-pressureseparators to further separate the monomers and other volatiles from theplasticized polymer blend to form a further-enriched plasticized polymerblend.
 13. The process of claim 12 further comprising feeding thefurther-enriched plasticized polymer blend to a coupled devolatilizer tofurther separate other volatiles from the further-enriched plasticizedpolymer blend to form a plasticized polymer product blend, wherein thecoupled devolatilizer operates under vacuum enabling thefurther-enriched plasticized polymer blend to flash off the monomers andother volatiles, and wherein the coupled devolatilizer is adevolatilizing extruder.
 14. The process of claim 13 wherein one or morepolymers, one or more off-line produced plasticizer and/or one or morepolymer additives are added to the plasticized polymer product blend atthe high-pressure separator, the low-pressure separator, thedevolatilizing extruder or combinations thereof.
 15. The process ofclaim 1 wherein the high-pressure separator is a gravimetric separationvessel, wherein the monomer-rich phase has a density of about 0.3 toabout 0.7 grams/mL and the polymer-rich phase has a density of about 0.4to about 0.8 grams/mL.
 16. The process of claim 14 wherein the one ormore off-line produced plasticizers are chosen from ethylene-basedpolyolefin oligomers, propylene-based polyolefin oligomers, butene-basedpolyolefin oligomers, higher alphaolefin-based polyolefin oligomers,paraffins, mineral oils, process oils, high purity hydrocarbon fluids,Group III lubricant basestocks, esters, propylene-rich soft polyolefins,ethylene-rich soft polyolefins, elastomeric soft polyolefins, propylenehomopolymers, propylene copolymers, butene-1 homopolymers, butene-1copolymers, isobutylene-based elastomers, thermoplastic vulcanizates andcombinations thereof.
 17. The process of claim 1 wherein the one or moreplasticizers comprise an ethylene-based polyolefin oligomer, apropylene-based polyolefin oligomer, a butene-based polyolefin oligomer,a higher-alphaolefin-based polyolefin oligomer, propylene-rich softpolyolefins, ethylene-rich soft polyolefins, elastomeric softpolyolefins, propylene homopolymers, propylene copolymers, butene-1homopolymers, butene-1 copolymers, isobutylene-based elastomers,thermoplastic vulcanizates and combinations thereof.
 18. The process ofclaim 17 wherein the propylene-rich soft polyolefins and ethylene-richsoft polyolefins have a Tg of −20° C. or less and a crystallinity of 15%or less.
 19. The process of claim 17 wherein the ethylene-basedpolyolefin oligomer has a Mn of 300 to 10,000 g/mol and a pour point of−20° C. or less.
 20. The process of claims 17 wherein thehigher-alphaolefin-based polyolefin oligomer has a Mn of 300 to 10,000g/mol and a pour point of −20° C. or less.
 21. The process of claim 1wherein the one or more plasticizers comprise from 0.25 wt % to 90 wt %of the plasticized polymer blend.
 22. The process of claim 1 wherein theone or more base polymers are chosen from HDPE, LDPE, LLDPE, vLDPE,isotactic PP, syndiotactic PP, ethylene-propylene random copolymer,ethylene-propylene plastomer, ethylene-propylene elastomer,ethylene-propylene impact copolymer, ethylene-propylene rubber,ethylene-propylene-diene terpolymer, ethylene-propylene-butene-1terpolymer, olefin block copolymers, poly(1-butene), styrenic blockcopolymer, butyl, halobutyl, thermoplastic vulcanizates and combinationsthereof.
 23. A in-line blending process for plasticized polymerscomprising: (a) providing two or more reactor trains configured inparallel and two or more high-pressure separators fluidly connected tothe two or more reactor trains configured in parallel, wherein one ormore of the reactor trains produces one or more base polymers and one ormore of the reactor trains produces one or more plasticizers; (b)contacting in the two or more reactor trains configured in parallel 1)olefin monomers having two or more carbon atoms 2) one or more catalystsystems, 3) optional one or more comonomers, 4) optional one or morescavengers, and 5) optional one or more diluents or solvents, wherein atleast one of the reactor trains configured in parallel is at atemperature above the solid-fluid phase-transition temperature of thepolymerization system and a pressure no lower than 10 MPa below thecloud point pressure of the polymerization system and less than 1500MPa, wherein the polymerization system for each reactor train is in itsdense fluid state and comprises the olefin monomers, any comonomerpresent, any diluent or solvent present, any scavenger present, and thepolymer product, wherein the catalyst system for each reactor traincomprises one or more catalyst precursors, one or more activators, andoptionally, one or more catalyst supports, wherein the one or morecatalyst systems are chosen from Ziegler-Natta catalysts, metallocenecatalysts, nonmetallocene metal-centered, heteroaryl ligand catalysts,late transition metal catalysts, and combinations thereof; (c) formingan unreduced polymer or unreduced plasticizer reactor effluent includinga homogenous fluid phase polymer-monomer mixture or plasticizer-monomermixture in each parallel reactor train; (d) passing the reactoreffluents from one or more of the parallel reactor trains through one ormore high-pressure separators, maintaining the temperature and pressurewithin the one or more high-pressure separators above the solid-fluidphase transition point but below the cloud point pressure andtemperature to form one or more fluid-fluid two-phase systems with eachtwo-phase system comprising a polymer-enriched phase orplasticizer-enriched phase and a monomer-rich phase, and separating themonomer-rich phase from the polymer-enriched phase orplasticizer-enriched phase in each of the one or more high-pressureseparators to form one or more separated monomer-rich phases, one ormore polymer-enriched phases or one or more plasticizer-enriched phases;(e) passing the one or more polymer-enriched phases and one or moreplasticizer-enriched phases from the one or more high-pressureseparators of (d), any unreduced polymer reactor effluents from the oneor more parallel reactor trains through another high-pressure separatorfor product blending and product-feed separation; (f) maintaining thetemperature and pressure within the another high pressure separator of(e) above the solid-fluid phase transition point but below the cloudpoint pressure and temperature to form a fluid-fluid two-phase systemcomprising a plasticized polymer-rich blend phase and a monomer-richphase; and (g) separating the monomer-rich phase from the plasticizedpolymer-rich blend phase in the high pressure separator to form aplasticized polymer blend and a separated monomer-rich phase.
 24. Anin-line blending process for plasticized polymers comprising: (a)providing two or more reactor trains configured in parallel, ahigh-pressure separator downstream fluidly connected to the two or morereactor trains configured in parallel, and one or more storage tanks,wherein the two or more reactor trains produce one or more base polymersand the one or more storage tanks store one or more off-line producedplasticizers; (b) contacting in the two or more reactor trainsconfigured in parallel 1) olefin monomers having two or more carbonatoms 2) one or more catalyst systems, 3) optional one or morecomonomers, 4) optional one or more scavengers, and 5) optional one ormore diluents or solvents, wherein at least one of the reactor trainsconfigured in parallel is at a temperature above the solid-fluid phasetransition temperature of the polymerization system and a pressure nolower than 10 MPa below the cloud point pressure of the polymerizationsystem and less than 1500 MPa, wherein the polymerization system foreach reactor train is in its dense fluid state and comprises the olefinmonomers, any comonomer present, any diluent or solvent present, anyscavenger present, and the polymer product, wherein the catalyst systemfor each reactor train comprises one or more catalyst precursors, one ormore activators, and optionally, one or more catalyst supports, whereinthe one or more catalyst systems are chosen from Ziegler-Nattacatalysts, metallocene catalysts, nonmetallocene metal-centered,heteroaryl ligand catalysts, late transition metal catalysts, andcombinations thereof; (c) forming an unreduced polymer reactor effluentincluding a homogeneous fluid phase polymer-monomer mixture in eachparallel reactor train; (d) passing the polymer reactor effluentcomprising the homogeneous fluid phase polymer-monomer mixture from eachparallel reactor train through the high-pressure separator for productblending and product-feed separation; (e) maintaining the temperatureand pressure within the high-pressure separator above the solid-fluidphase transition point but below the cloud point pressure andtemperature to form a fluid-fluid two-phase system comprising apolymer-rich blend phase and a monomer-rich phase; (f) separating themonomer-rich phase from the polymer-rich blend phase in the highpressure separator to form a polymer blend and a separated monomer-richphase; and (g) feeding the one or more off-line produced plasticizersfrom the one or more storage tanks to the process after (c) to form aplasticized polymer blend.
 25. A in-line blending process forplasticized polymers comprising: (a) providing two or more reactortrains configured in parallel and two or more high-pressure separatorsfluidly connected to the two or more reactor trains configured inparallel, and one or more storage tanks, wherein two or more of thereactor trains produce one or more base polymers and the one or morestorage tanks store one or more off-line-produced plasticizers; (b)contacting in the two or more reactor trains configured in parallel 1)olefin monomers having two or more carbon atoms 2) one or more catalystsystems, 3) optional one or more comonomers, 4) optional one or morescavengers, and 5) optional one or more diluents or solvents, wherein atleast one of the reactor trains configured in parallel is at atemperature above the solid-fluid phase-transition temperature of thepolymerization system and a pressure no lower than 10 MPa below thecloud point pressure of the polymerization system and less than 1500MPa, wherein the polymerization system for each reactor train is in itsdense fluid state and comprises the olefin monomers, any comonomerpresent, any diluent or solvent present, any scavenger present, and thepolymer product, wherein the catalyst system for each reactor traincomprises one or more catalyst precursors, one or more activators, andoptionally, one or more catalyst supports, wherein the one or morecatalyst systems are chosen from Ziegler-Natta catalysts, metallocenecatalysts, nonmetallocene metal-centered, heteroaryl ligand catalysts,late transition metal catalysts, and combinations thereof, (c) formingan unreduced polymer reactor effluent including a homogenous fluid phasepolymer-monomer mixture in each parallel reactor train; (d) passing thereactor effluents from one or more of the parallel reactor trainsthrough one or more high-pressure separators, maintaining thetemperature and pressure within the one or more high-pressure separatorsabove the solid-fluid phase transition point but below the cloud pointpressure and temperature to form one or more fluid-fluid two-phasesystems with each two-phase system comprising a polymer-enriched phaseand a monomer-rich phase, and separating the monomer-rich phase from thepolymer-enriched phase in each of the one or more high-pressureseparators to form one or more separated monomer-rich phases and one ormore polymer-enriched phases; (e) passing the one or morepolymer-enriched phases from the one or more high-pressure separators of(d), any unreduced polymer reactor effluents from one or more parallelreactor trains through another high-pressure separator for productblending and product-feed separation; (f) maintaining the temperatureand pressure within the another high pressure separator of (e) above thesolid-fluid phase transition point but below the cloud point pressureand temperature to form a fluid-fluid two-phase system comprising apolymer-rich blend phase and a monomer-rich phase; (g) separating themonomer-rich phase from the polymer-rich blend phase in the highpressure separator to form a polymer blend and a separated monomer-richphase; and (h) feeding the one or more off-line produced plasticizersfrom the one or more storage tanks to the process after (c) to form aplasticized polymer blend.